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
• • 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 glass threads or fibers, in particular intended for reinforcing organic and / or inorganic materials and usable as textile threads, these threads being capable of being produced by a process consisting in mechanically stretching molten glass fillets. flow of orifices arranged at the base of a die.
• the field of reinforcing glass wires is a particular field of the glass industry. These yarns are prepared from specific glass compositions, the glass used to be stretched in the form of filaments of a few micrometers in diameter, according to the method described above, and to allow the formation of son able to fulfill in particular their role of reinforcement .
• the most commonly used reinforcing glass yarns are thus glass yarns whose composition derives from the eutectic composition of the ternary SiO 2 -Al 2 Os-CaO diagram whose liquidus temperature is 1170 ° C.
• E-glass yarns These yarns are referred to as "E-glass” yarns, the archetype of which is described in US-A-2 334 961 and US-A-2 571 074, and which have a substantially basic composition.
• silica, alumina, lime and boric anhydride present at levels ranging from 5 to 13% in glass compositions known as “glass E”, is added to replace the silica in order to reduce the liquidus temperature of the formed glass and to facilitate its melting.
• glass E glass compositions known as “glass E”
• the term “liquidus temperature” denoted “T ⁇ q ", is the temperature at which the most refractory crystal appears in a system with thermodynamic equilibrium. The liquidus temperature therefore gives the lower limit to which it is possible to fiber.
• the forming margin is defined as the difference between the temperature at which the viscosity of the glass is 1000 Poises (100 Pa. S), the temperature at which the glass is generally fiber and noted "T3" in the rest of the text, and the liquidus temperature.
• E glass son are further characterized by a content of alkaline oxides (essentially Na 2 O and / or K 2 O) limited.
• compositions without boron or fluorine formed essentially from the quaternary system SiO 2 -Al 2 ⁇ 3 -CaO-MgO, containing small amounts of titanium oxide (less than 0.9%).
• the described compositions which include the composition of the fiber sold under the name Advantex TM by the company Owens Corning, are characterized in terms of their properties by a high specific Young's modulus, a high forming margin and a higher T3 temperature. than that of glass E. Considerations related to the interaction between the glass strands and the human or animal body have also been developed.
• the mineral fibers are indeed susceptible, when certain geometric criteria in terms of diameter and / or length are respected, to be introduced by inhalation into the body and in particular into the lungs, sometimes to the pulmonary alveoli. These considerations have been mainly developed in the field of mineral wools used for thermal or acoustic insulation, because the length and diameter of these fibers are quite low.
• glass strands capable of reinforcing organic or inorganic materials are generally continuous (strands, textile threads, etc.) or, when they are cut, have a length greater than 3 mm, which is much too high for to enter the body by air.
• the diameter of the son which consist of several individual filaments
• WO 03/050054 discloses glass yarns whose chemical composition has been adjusted (essentially by addition of Al 2 O 3 alumina) to render the fibers biosoluble. Nevertheless, the forming margin of these fibers makes them unfit to be fibered by a process consisting of mechanically stretching molten glass threads flowing from orifices arranged at the base of a die.
• the application WO 2006/103376 describes mineral fibers, and in particular glass strands that can be obtained by a process consisting in mechanically stretching threads of molten glass flowing from orifices arranged at the base of a spinneret, of which the biosolubility has been improved.
• the chemical composition of these glass strands makes them capable of being obtained by a mechanical drawing process, in particular by the addition of sodium oxide in large quantities (at least 14% by weight). These compositions however contain boron oxide.
• the aim of the invention is to propose glass strands that can be obtained by a process consisting of mechanically stretching molten glass threads flowing from orifices arranged at the base of a spinneret whose chemical composition has properties similar to those obtained by the glass strands described in the application WO 96/39362, in particular in terms of chemical durability, specific Young's modulus, temperature T3 and forming margin, while having a high dissolution rate in physiological medium, particularly in pulmonary fluids.
• Another object of the invention is to provide glass compositions that cause low emissions that are harmful to the environment when they are melted.
• the subject of the invention is glass strands that can be obtained by a process consisting in mechanically stretching molten glass threads flowing from orifices arranged at the base of a spinneret, the chemical composition of which is substantially free of boron oxide and comprises the following constituents within the limits defined below expressed in percentages by weight:
• composition of the glass strands according to the invention is substantially free of boron oxide B 2 ⁇ 3. This means that it does not contain boric anhydride, with the exception of any impurities (usually less than 0.05% or even 0.01%) from the raw materials used.
• Silica is a forming oxide of the vitreous network, and plays an essential role for its stability. Within the limits defined above, when the percentage of this constituent is less than 40%, the glass obtained is not sufficiently viscous and devitrifies too easily during fiber drawing. For contents above 50% (and in view of the high content of alumina) the glass becomes very viscous and difficult to melt, and the liquidus temperature increases, the forming margin decreasing to negative and preventing drawing by mechanical stretching. In addition, high levels of SiO 2 penalize the biosolubility properties of the fibers. As a result, the silica content is preferably less than or equal to 49%, and particularly preferably less than or equal to 48%.
• silica plays a beneficial role essential for improving the Young's modulus, its content is preferably greater than or equal to 42%, 43%, even 44% and even 45% or 46%. A particularly preferred compromise is to choose a silica content between 46 and 48%.
• Alumina (Al 2 Os) is also a formator of the glass network according to the invention and plays a fundamental role in their stability.
• a content of less than 18% causes a significant increase in the hydrolytic attack of the glass and a too low biosolubility, whereas the increase of the percentage of this oxide above 28% results in devitrification risks and an increase too much viscosity and therefore the temperature T3.
• the alumina content is preferably less than or equal to 27%, or even 26% or 25%, especially 24% or 23%. It has also been observed that above a certain threshold, high levels of alumina are detrimental to high biosolubility.
• the alumina content is preferably greater than or equal to 19% or even 20%.
• An interesting optimum for combining the beneficial properties of alumina is between 20 and 23%.
• the sum of the silica and alumina contents, denoted SiO 2 + AbOs, is preferably greater than or equal to 66%, even 68% and / or less than or equal to 75% or even 72%.
• Lime (CaO) and magnesia (MgO) make it possible to adjust the viscosity and control the devitrification of the glasses according to the invention, which greatly influences the forming margin.
• a CaO content greater than or equal to 15% causes an increase in liquidus temperature preventing drawing by mechanical drawing.
• a CaO content of less than 4% leads to too low hydrolytic resistance.
• the CaO content is therefore preferably greater than or equal to 5%, especially 6% and / or less than or equal to 14%, even 12% or 11%, and even 10% or 9.5% or even 9%, the effect of CaO on the increase of the liquidus temperature.
• An optimal content of CaO is between 6 and 10%, or even between 6 and 9%.
• the MgO content is preferably greater than or equal to 1%, even 2% and even 3% or 4% and / or less than or equal to 5%.
• the sum of the contents of CaO and MgO is preferably less than or equal to 15%, even 14% or even 13%.
• the oxides of barium (BaO) and strontium (SrO) contribute to significantly increase the cost of glass. Their individual content is therefore preferably less than or equal to 5%, or 2%, and even 1%, or even zero.
• the alkaline oxides are indispensable in the compositions according to the invention for rendering the glass capable of being fiber by a drawing process mechanical.
• the glasses described in the application WO 96/39362 do not contain alkaline oxides, or at very low levels, but may nevertheless be fibers by mechanical stretching thanks to the high CaO contents (at least 20%).
• the CaO content must be limited so as not to degrade the liquidus temperature too much.
• Sodium oxide (Na 2 O) is introduced at a level of at least 10%, because for lower contents, the liquidus temperature is too high and increases faster than the viscosity of the glass, thus reducing the margin from forming to making it negative and thus preventing drawing by mechanical stretching.
• contents of more than 14% as described in the above-mentioned application WO 2006/103376, it appeared to the inventors that the viscosity decreased faster than the liquidus temperature, certainly reducing the temperature at which the strands can be obtained but also reducing the forming margin, making it necessary to add boron oxide to obtain an adequate forming margin.
• the invention is therefore partly based on the fact that there is a restricted range of Na 2 O contents in which boron-free glass strands can be obtained by mechanical drawing with good fiber drawing quality.
• the sodium oxide content is preferably greater than or equal to 11%, especially 11.5% or even 12%, and / or less than or equal to 13.5%.
• Potassium oxide (K 2 O) also has the advantage of increasing the forming margin by having a strong action of reducing the liquidus temperature. Given its high cost, the potassium oxide is advantageously present at levels greater than or equal to 1%, even 2% and even 3% or 4% and / or less than or equal to 8%, or even 7% or 6% or 5%.
• the content of lithium oxide (Li 2 O) is preferably maintained below 0.5%, and preferably below 0.1%, or even 0.05% or 0.01%.
• the total content of alkaline oxides (Na 2 O + K 2 ⁇ + Li 2 ⁇ ) is less than or equal to 20%, since above this value, the hydrolytic resistance and the Young's modulus are clearly degraded, as well as the cost of the glass.
• This total content of alkaline oxides is preferably less than or equal to
• the total content of alkaline oxides is preferably greater than or equal to 14%.
• TiO 2 is known as a fluidifying agent for glass and may reduce the liquidus temperature. Above 1%, the yellow color and the extra cost it generates may become unacceptable for certain applications.
• the titanium oxide content of the glasses according to the invention is preferably less than or equal to 1%, or even 0.9%, and even 0.8%. Given its favorable action on the resistance of glass son in acid medium, its content may advantageously be greater than or equal to 0.5%.
• Zinc oxide makes it possible to reduce the viscosity of the glasses according to the invention and to increase their resistance to corrosion in an acid medium. However, given the high price of this oxide, its content is preferably less than or equal to 0.4%, preferably less than or equal to 0.1%, or even less than 0.05% or 0.01%.
• Zirconium oxide (ZrO 2 ) is capable of improving the resistance in acid medium of the glass strands according to the invention. For this reason, a content greater than or equal to 0.5% may be appreciable. However, given its unfavorable role on the devitrification of glass, a content of less than or equal to 1% is preferred.
• the manganese oxide content is preferably less than 1%, and preferably less than 0.3%. Since this oxide is capable of giving the glass a very intense purple coloration, the MnO content is preferably maintained below 0.1%, or even 0.05% and even 0.01%.
• Fluorine may be added in small amounts to enhance melting of the glass, or be present in the impurity state. It has been discovered, however, that small amounts of fluorine very clearly affect the temperature resistance of the glasses according to the invention.
• the fluorine content is therefore advantageously maintained below 0.5%, and especially less than 0.1%, or even zero, in particular for environmental reasons.
• Iron oxide is an unavoidable impurity of the glasses according to the invention because of its presence in several raw materials, and its content is generally less than 0.5%. Since the staining effect generally attributed to titanium is in fact due to an electronic transfer between the Fe 2+ and Ti 4+ ions, the iron content in the glasses according to the invention is advantageously less than 0.3%. , especially at 0.2%, thanks to a judicious choice of raw materials.
• the sum of the contents of SiO 2 , Al 2 O 3 , CaO, MgO, Na 2 O and K 2 O is greater than or equal to 95%, preferably 96% or 97%, or even 98% or 99% .
• One or more other components may also be present, generally as impurities, in the chemical composition of the yarns according to the invention, the total content of these other components generally remaining less than or equal to 5%, preferably less than 2%.
• the rate of each of these other components not generally exceeding 0.5%. It may be in particular agents used to refine the glass (eliminate gaseous inclusions) such as sulfur, or compounds from the dissolution in the glass of small amounts of materials used as refractory in the melting furnace. glass. These different impurities do not modify the manner in which the glass threads described above solve the technical problem underlying the invention.
• the glass yarns according to the invention can be made and implemented like E glass or Advantex TM glass yarns.
• the glass strands according to the invention are preferably obtained from the glasses of composition previously described according to the following method: a multiplicity of molten glass threads, flowing from a multiplicity of orifices dispersed at the base of a or more dies are drawn in the form of one or more continuous filament webs and then gathered into one or more yarns collected on a moving support. It can be a support rotating when the son are collected in the form of windings or a support in translation when the son are cut by a member also serving to stretch or when the son are projected by an organ used to stretch them so to form a mat.
• the subject of the invention is therefore also a method for manufacturing the glass yarns according to the invention, comprising the drawing steps in the form of one or more continuous filament webs of a multiplicity of molten glass threads. flowing from a plurality of orifices arranged at the base of one or more dies, and assembling said filaments into one or more yarns collected on a moving support.
• the glass threads according to the invention can also be obtained by a so-called “staple” process, in which glass threads flowing from a spinneret are stretched by means of jets of compressed air, the discontinuous filaments thus obtained falling in rain on a drum then being collected to form a thread.
• This wire has a structure different from that obtained by mechanical stretching and is in the form of a wick of discontinuous filaments substantially parallel and without torsion.
• the son obtained possibly after other processing operations, can thus be in various forms: continuous son, cut son, braids, ribbons, mats, networks ..., these son being composed of filaments of diameter ranging from 5 at about 30 micrometers.
• the yarns according to the invention can in particular be in the following forms, among which are, by way of example and in a nonlimiting manner:
• crushed yarns obtained by grinding of base yarns, the length then typically varying between 0.1 and 0.5 mm,
• the fabrics either continuous yarn or chopped yarn, in which the yarns are distributed without intentional orientation and chemically bonded together or entangled with a needlecraft (needled mat), the fabrics, together rovings or yarns having undergone at least one twist (single, multiple or cabled yarn) obtained by means of a loom weaving and composed of a warp and a weft, - the sails obtained by papermaking process from cut threads.
• the molten glass feeding the dies is obtained from raw materials possibly pure (for example from the chemical industry) but most often natural, the latter sometimes including trace impurities, these raw materials being mixed in. appropriate proportions to obtain the desired composition, and then being melted.
• the temperature of the molten glass (and therefore its viscosity) is set in the traditional way by the operator so as to allow the fibering of the glass, avoiding in particular the problems of devitrification and so as to obtain the best possible quality of the glass son.
• the filaments are generally coated with a sizing composition that makes it possible to protect them from abrasion and to facilitate their subsequent association with materials to be reinforced.
• the composites obtained from the yarns according to the invention comprise at least one organic material and / or at least one inorganic material and glass yarns, at least a portion of the yarns being the glass yarns according to the invention.
• the invention therefore also relates to a composite of glass son and organic (s) and / or inorganic (s) comprising glass son according to the invention.
• the glass yarns according to the invention may have already been associated, for example during drawing, with filaments of organic material so as to obtain composite yarns.
• glass yarn whose composition comprises " means according to the invention "son formed from glass filaments whose composition comprises ", the glass filaments being optionally associated with organic filaments before gathering the filaments into yarns.
• the glass yarns according to the invention can also be used for the lining of automobile exhaust pipes.
• the glass strands according to the invention confer good sound insulation properties, but are also subject to temperatures that may exceed 850 0 C or even 900 0 C.
• Table 1 gathers four examples according to the invention numbered from 1 to 4, and two comparative examples, numbered C1 and C2.
• C1 is an Advantex TM type glass composition derived from the teaching of application WO 96/39362.
• C2 is an example from the application WO 03/050054.
• the composition of the glasses is expressed in mass percentages of oxides.
• Table 1 has the following properties: the temperature corresponding to a viscosity of 10 3 poise (100 Pa ⁇ s), denoted T3, measured according to ISO 7884- 2 and expressed in degrees
• DSG is expressed in mg and corresponds to the mass of dry residue, expressed in mg / 10 g of glass.
• the rate of dissolution in an acid medium denoted “kSi ⁇ 2 ", representing the rate of dissolution of fibers with a diameter of 10 microns left 6 hours in static saline buffered at a pH of 4.5.
• the saline solution contains, in addition to the pH buffer, sodium chloride and sodium citrate in concentrations of 5g / L and 0.15g / L respectively, the ratio of the exposed glass surface to the volume of the aqueous solution. attack is 0.5 cm "1.
• This dissolution rate expressed in ng / cm 2 .h, expresses the amount of glass dissolved per fiber and surface time units.
• Examples 1 to 4 according to the invention have properties similar to those of Example C1 in terms of fiberizing temperature, forming margin, specific modulus or hydrolytic resistance. They present also a very improved forming margin with respect to Example C2, which can not be properly fiber by mechanical drawing due to a negative forming margin.
• the forming margin of the glasses according to the invention greater than 50 ° C., and possibly even up to 94 ° C. (eg 3), guarantees, on the other hand, a fiber formation of very good quality.
• the biosolubility of the glasses according to the invention is also very satisfactory.

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• 2007
  • 2007-06-27 FR FR0756068A patent/FR2918053B1/fr not_active Expired - Fee Related
• 2008
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  • 2008-06-25 CN CN200880021688A patent/CN101715432A/zh active Pending
  • 2008-06-25 EA EA201070064A patent/EA018315B1/ru not_active IP Right Cessation
  • 2008-06-25 WO PCT/FR2008/051152 patent/WO2009007599A1/fr active Application Filing
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