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
  • C03C13/00—Fibre or filament compositions
  • C03C13/06—Mineral fibres, e.g. slag wool, mineral wool, rock wool
• • 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
  • C03C2213/00—Glass fibres or filaments
  • C03C2213/02—Biodegradable glass fibres

Definitions

• the present invention relates to the field of artificial mineral wools. It relates more particularly to mineral wools intended for manufacturing thermal and / or acoustic insulation materials or soilless growing substrates.
• this type of mineral wool can be fiber by so-called "external" centrifugation processes, for example of the type of those using a cascade of centrifugation wheels fed with molten material by a static distribution device, as described in particular in the patents EP-0 465 31 0 or EP-0 439 385.
• the object of the invention is therefore to improve the chemical composition of mineral wools of the rock or basalt type, an improvement aimed in particular at increasing their biodegradable nature and / or at reconciling a biodegradable character with an ability to be fiberized by external centrifugation (without excluding however other fiberizing modes).
• the subject of the invention is a mineral wool capable of dissolving in a physiological medium, which comprises the following constituents according to the following weight percentages:
• composition has made it possible to combine a whole series of advantages, in particular by playing on the multiple, complex roles played by a certain number of its specific constituents.
• the fiber viscosity of such a composition is suitable for external centrifugation.
• P 2 O 5 is not without influence on the viscosity of the composition, like alumina.
• the viscosimetric behavior of the composition is an important criterion to control.
• certain compounds can be advantageous for certain properties and yet be unfavorable for a high biodegradability, which appears to be the case with iron, advantageous for example to give mineral wool good fire resistance, but which could tend to reduce the biodegradability of rock wool, or the case of alumina, which is judicious for regulating the viscosity of the composition but which may not be very favorable with regard to biosolubility, in particular measured by in vitro tests at pH neutral.
• the composition may contain P 2 O 5 , but in a moderate content of at most 5%, and rather at most 4% . It also contains at least a low content of iron oxide, which may prove advantageous (or inevitable in trace amounts) but for reasons other than biodegradability. However, it achieves a high level of biodegradability without excessive addition of P 2 0 5 or even without P 2 O 5 at all (or any other very particular compound assumed to be favorable to biodegradability), by another means, which has consisted, in particular, in to play on the relative proportion in MgO compared to CaO.
• rock-type compositions contain a CaO lime content very much higher than that of MgO magnesia. It turned out that by modifying this report, we managed to reach the high level of biodegradability which until now could only be obtained with high P 2 0 5 contents in order to "compensate" for significant alumina and / or iron contents. Note a non-negligible subsidiary advantage linked to a low P 2 0 5 level : too much P 2 0 5 tends to increase the liquidus temperature of the composition.
• Another characteristic feature according to the invention relates to the combination of this particular MgO / CaO ratio with a fairly high level of alumina, since at least 16%. It turned out that this combination made it possible to satisfactorily meet the criteria of biosolubility, as well measured according to in vitro tests at neutral pH as according to in vitro tests at acid pH. Indeed, it has not been decided definitively on the point of knowing which pH was the most representative of the physiological medium in vivo, notably that of the pulmonary regions. A high level of alumina previously seemed to be favorable to rapid dissolution at an acid pH but not at neutral pH.
• the invention makes it possible to obtain a high level of biosolubility, at least measured in vitro, whatever the pH, by selecting a high level of alumina, but in particular by adapting the content of alkaline earth oxides so as to retain its beneficial effect at acidic pH without being penalizing at neutral pH.
• the sum Si0 2 + AI 2 O 3 makes it possible to regulate for a large part the viscosimetric behavior of the compositions and that it is preferably at least 58%, in particular between 59 and 64%.
• the mineral wool compositions according to the invention contain an RO content of alkaline earth oxides (CaO and / or MgO) either between 1 8 and 32%, or more than 32% up to 40%, for example between 26 and 30%.
• CaO and / or MgO alkaline earth oxides
• the iron contents Fe 2 0 3 can be, according to a first very moderate variant, from 0.5 to 1.7% in particular (generally combined with a high RO content, greater than 32%). This low content makes it possible to obtain what is sometimes referred to as "white wool", used in particular for applications of mineral wool by spraying on building elements.
• the iron content is higher, with in particular more than 1.7% up to 12% in Fe 2 0 3 , and preferably from 5 to 10% or from 5 to 8% Fe 2 0 3 (generally combined with an RO content of 1 8 to 32%).
• iron in particular makes it possible to impart good fire resistance to mineral wools.
• the mineral wool is generally assembled in felts.
• the content of oxides R 2 0 Na 2 0 and / or K 2 0
• the content of oxides R 2 0 can be either between 0.3 and 1% (preferably with a view to manufacturing the white wool mentioned above), or higher, in particular from more than 1% to almost 6%, for example from at least 2 to 2.2% or between 1 and 3%.
• compositions according to the invention also respect the following relationship, expressed in a ratio of weight percentages: MgO / CaO greater than 0.85, in particular greater than 0.95 or 1 or 1, 1 5, and generally at least plus 2 or 3.
• MgO / CaO greater than 0.85, in particular greater than 0.95 or 1 or 1, 1 5, and generally at least plus 2 or 3.
• compositions according to the invention can respect the relationship R 2 O / AI 2 O 3 of between 0.07 and 0.8, preferably between 0.09 and 0.3 or between 0.05 and 0.2 .
• compositions according to the invention preferably have a P 2 O 5 content of more than 0.1%, and in particular up to 2 to 3%. This moderate rate influences the biodegradability very advantageously, without penalizing the composition economically too much or influencing its liquidus temperature too much.
• the level of P 2 0 5 can be lower, in particular be zero or slightly higher up to 0.1%.
• the oxidation of the composition can for example be controlled by the optional addition of manganese oxide MnO, in particular in a content of 0.1 to 4%.
• Adding boron oxide, which is also optional and in particular of a content of 0.1 to 5%, can make it possible to improve the thermal insulation properties of mineral wool, in particular by tending to lower its coefficient of thermal conductivity in its radiative component.
• the composition can also contain TiO 2 as impurities or added voluntarily, for example in a content up to 1 to 2%.
• SO 3 is also to be considered as an impurity, just like P 2 0 5 when it is confined to values less than 0.1% in particular.
• the preferential CaO content of the composition according to the invention is less than or equal to 22%, in particular at least 1 0%, advantageously between 1 1 and 1 8% or more than 1 8 to 21%.
• the preferential level of MgO of the composition is preferably at least 11% and generally at most 19%, the preferred range being between 12 and 15%.
• the alumina Al 2 0 3 content of the compositions is at least 18.5%, in particular at least 19%, and even at least 20 or 21 %.
• the difference T, ogl - T q is preferably at least 10 ° C, preferably at least 20 or 30 ° C: this difference defines the "working level" of the compositions of the invention, it is that is to say the range of temperatures in which they can be fiberized, by external centrifugation in particular.
• Mineral wools exhibit a satisfactory level of biosolubility, whether the measurement method involves a neutral, slightly basic pH, or an acidic pH.
• the mineral wools according to the invention thus generally have a dissolution rate of at least 30, and preferably at least 40 and even at least 50 ng / cm 2 per hour (in particular measured on silica) measured at pH 4.5 and at least 30, and preferably at least 40 and even at least 50 ng / cm 2 per hour (in particular measured on silica) measured at pH 7.5.
• They also generally have a dissolution rate of at least 30, and preferably at least 40 and even 50 ng / cm 2 per hour measured at pH 4.5 and a dissolution rate of at least 30, and preferably at least 40 and even s 50 ng / cm 2 per hour measured at pH 6.9 (always in particular measured on silica). They generally also have a dissolution rate of at least 60, in particular at least 80 ng / cm 2 per hour measured at pH 7.5 and / or a dissolution rate of at least 40 ng / cm 2 , in particular at least
• Table 1 below groups together the chemical compositions, in weight percentages, of fifteen examples.
• the residual level corresponds to the non-analyzed impurities / minority components, a level of at most 0.5% to 1% and / or is only due to the approximation accepted in this area in the analysis methods used.
• compositions according to these examples were fiberized by external centrifugation, in particular according to the teaching of the aforementioned patents.
• Table 2 below groups together the results of measurements of the speed of dissolution of silica in mineral wools according to examples 9, 10 and 11, denoted “K S
• compositions 1 6 and 1 7 Two examples of additional compositions 1 6 and 1 7 also proved to be interesting, respecting the formulation described above with an MgO / CaO ratio of 0.75.
• compositions are detailed in Table 3 below with the same concentrations as in Table 1: 11

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• General Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Glass Compositions (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Cultivation Of Plants (AREA)
• Hydroponics (AREA)

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• 1998
  • 1998-05-06 FR FR9805707A patent/FR2778400A1/fr active Pending
• 1999
  • 1999-05-04 WO PCT/FR1999/001056 patent/WO1999056526A1/fr not_active Application Discontinuation
  • 1999-05-04 SK SK1889-99A patent/SK188999A3/sk unknown
  • 1999-05-04 EP EP99916985A patent/EP0994648A1/fr not_active Withdrawn
  • 1999-05-04 PL PL99337923A patent/PL337923A1/xx unknown
  • 1999-05-04 TR TR2000/00072T patent/TR200000072T1/xx unknown
  • 1999-05-04 BR BR9906422-7A patent/BR9906422A/pt not_active Application Discontinuation
  • 1999-05-04 AU AU35275/99A patent/AU3527599A/en not_active Abandoned
  • 1999-05-04 HU HU0002499A patent/HUP0002499A2/hu unknown
  • 1999-05-04 JP JP2000546574A patent/JP2002512817A/ja active Pending
  • 1999-05-04 CA CA002295870A patent/CA2295870A1/fr not_active Abandoned
  • 1999-05-04 CN CN99801073.1A patent/CN1273505A/zh active Pending
  • 1999-05-05 AR ARP990102110A patent/AR015287A1/es unknown
  • 1999-12-28 IS IS5326A patent/IS5326A/is unknown
• 2000
  • 2000-01-05 HR HR20000009A patent/HRP20000009A2/hr not_active Application Discontinuation
  • 2000-01-05 NO NO20000029A patent/NO20000029L/no not_active Application Discontinuation
  • 2000-01-11 ZA ZA200000071A patent/ZA200000071B/xx unknown

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