EP1098858A1 - Synthetische glasfasern - Google Patents

Synthetische glasfasern

Info

Publication number
EP1098858A1
EP1098858A1 EP99932758A EP99932758A EP1098858A1 EP 1098858 A1 EP1098858 A1 EP 1098858A1 EP 99932758 A EP99932758 A EP 99932758A EP 99932758 A EP99932758 A EP 99932758A EP 1098858 A1 EP1098858 A1 EP 1098858A1
Authority
EP
European Patent Office
Prior art keywords
fibres
amount
product according
composition
feo
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP99932758A
Other languages
English (en)
French (fr)
Inventor
Marianne Guldberg
Soren Lund Jensen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rockwool AS
Original Assignee
Rockwool International AS
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 Rockwool International AS filed Critical Rockwool International AS
Publication of EP1098858A1 publication Critical patent/EP1098858A1/de
Withdrawn legal-status Critical Current

Links

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
    • C03C2213/00—Glass fibres or filaments
    • C03C2213/02—Biodegradable glass fibres

Definitions

  • the present invention concerns man-made vitreous fibres (MMVF) , which have a solubility in biological fluid (biosolubility) which is considered to be acceptable, which are durable in use and which give good fire resistance properties.
  • MMVF man-made vitreous fibres
  • MMV fibres from mineral melt.
  • a combination of raw materials is melted in a furnace to provide a mineral melt having the desired chemical composition and is then formed into fibres. These are used for various purposes including heat insulation, fire protection, sound insulation etc.
  • MMV fibres which can be said to be of improved biological safety.
  • Biological safety is usually measured on the basis of an in vitro test which assesses the dissolution rate of the fibres in a liquid which is intended to simulate lung liquid, such as Gamble's solution at about pH 7.5.
  • fibres disclosed in, in particular, W095/21799 have proved to be interesting and valuable as fibres which are soluble in biological media
  • improved biological solubility In particular there is a desire to achieve improved biological solubility when determined by in vivo tests. It is also desirable to achieve this biological solubility together with ease and efficiency of manufacture and with good physical properties of the fibres.
  • one method for determining biosolubility is by intra-tracheal tests, as described e.g.
  • a T 50 of less than or equal to 65 days is normally satisfactory at present but it would be desirable to produce fibres having even lower T 50 .
  • a product comprising man-made vitreous fibres formed from a composition which includes, by weight of oxides,
  • this particular combination of components in the defined amounts in particular the selected ranges of FeO, Al 2 0 3 and alkali metal (Na 2 0 + K 2 0) , especially the narrow range of FeO, give a good combination of durability in use and biosolubility. It is particularly surprising that biosolubility can be obtained with the very low levels of alkali metal, since these elements tend to enhance biosolubility.
  • the fibres can be produced from readily available starting materials and the fibres have good thermal stability, fire resistance and insulation properties.
  • the amount of Si0 2 is from 46 to 58%. Usually it is at least 50%, preferably at least 54%. In some cases it can be preferred that Si0 2 is not more than 56%.
  • the amount of A1 2 0 3 is from 0.8 to 3%. Usually it is at least 0.9 or at least 1%. In some cases it may be at least 1.1%. In general it is not more than 2.5%, preferably not more than 2%.
  • the amount of FeO is from 5 to 6.8%. In particular it is often at least 5.5%.
  • the iron should mainly be in the ferrous state (rather than in the ferric state) .
  • at least 70%, more preferably at least 80%, of the iron is ferrous.
  • at least 90 or 95% by weight of the iron is present in ferrous form in the product of the invention.
  • the amount of Ti0 2 is not more than 4%. It may be at least 0.2%, preferably at least 0.5%. In some compositions it can be at least 0.8 or 1%. It is generally not more than 2% and preferably not more than 1.5%. In some cases it is preferably not more than 0.5 or 0.2%.
  • the amount of CaO is from 0 to 40%. Generally it is at least 10%, preferably at least 15%. In general it is not more than 30 or 25%. It can be not more than 20% but in some cases amounts of at least 20% are beneficial, in particular if MgO is below 10 or 8%.
  • the amount of MgO is from 0 to 30%. It may be at least
  • the total amount of alkali metal (Na 2 0 + K 2 0) in the invention is very low and ranges from 0 to 1%. In particular it is not more than 0.8%, preferably not more than 0.6%. Generally the amount of Na 2 0 + K 2 0 is at least 0.1%, and can be at least 0.2%, although in some preferred cases it is particularly low and is below 0.2%.
  • the fibres must contain P 2 0 5 . It is present in an amount of 0.2 to 10%. In some fibres preferred according to the invention the amount is not more than 5%, preferably not more than 4%.
  • the amount of P 2 0 5 can preferably be not more than 2%. In these cases it is particularly surprising that we obtain good biosolubility properties, since it has been stated in various publications that the inclusion of a high amount of P 2 0 5 is required to achieve good biosolubility.
  • the amount of P 2 0 5 is preferably at least 0.5%.
  • the amount of P 2 0 5 can in some cases be from 0.2 to 3%. In other preferred compositions the amount of P 2 0 5 is at least 4%.
  • the ratio of P 2 0 5 / (A1 2 0 3 + FeO) is preferably not more than 0.8, more preferably not more than
  • solubility (based on wt.% of each oxide) is at least 25. Preferably it is at least 30, more preferably at least 31, most preferably at least 32 or 33. It may in particular be at least 34. This is necessarily an approximation and solubility should be determined experimentally using an appropriate protocol, but we find in general that as the value of this sum increases, the solubility of the fibres can increase.
  • the fibres in the product of the invention may contain various other elements in a total amount up to 10%.
  • the amount of other elements is not more than 6%, more preferably not more than 3% and in particular not more than 2%.
  • Other elements which can be contained in the fibres include B 2 0 3 , BaO, Zr0 2 , MnO, ZnO, F, Cl, Cr 2 0 3 and V 2 0 5 . If B 2 0 3 is present it is usually present in an amount of not more than 5%. In particular the amount of B 2 0 3 is preferably less than the amount of P 2 0 5 .
  • melt viscosity is viscosity in poise at 1400°C, measured by rotation viscometry or calculated according to Bottinga and Weill, American Journal of Science, Volume 272, May 1972, pages 455 to 475. Since P 2 0 5 is not included in this calculation the presence of P 2 0 5 is taken into consideration by equalising 1 mole % of P 2 0 5 with 2 mole % Si0 2 plus 1 mole % CaO. Laboratory tests have shown that this approximation is valid within actual chemical ranges.
  • the composition of the invention preferably provides a melt which has viscosity at 1400°C at least 10 poise, preferably at least 15 poise and often at least 17 poise. Although it may be as high as 60 poise, generally it is not more than 40 poise and preferably is not more than 30 poise. The range of 24 to 28 poise is advantageous.
  • the viscosity can be not more than 25 poise and in particular not more than 20 poise.
  • biosolubility is measured in terms of dissolution rate in Gamble's solution.
  • Dissolution rate is determined by a flow-through technique, as follows.
  • the modified Gamble's solution used has the following composition : all
  • the fibre diameter distribution is determined for each sample by measuring the diameter of at least 200 individual fibres by means of the intercept method and a scanning electron microscope or optical microscope (100 x magnification) .
  • the readings are used for calculating the specific surface of the fibre samples, taking into account the density of the fibres.
  • the calculations are based on the Si0 2 content in the fibres, the specific surface and the dissolved amount of Si.
  • the dissolution rate by the flow-through method is determined as follows. lO g of fibres are placed in a flow cell in a polycarbonate filter holder (diameter, 40 mm) .
  • 0.8 ⁇ m filter is placed on the inlet side (top) and a 0.2 ⁇ m filter is placed on the outlet side (bottom) to avoid loss of fibres during the test. Both filters are made of cellulose nitrate.
  • the flow rate of the modified Gamble's solution is around 200ml/day and is maintained at this rate by a peristaltic pump.
  • the ratio of liquid flow to surface area of the fibres is 1 to 2 ⁇ m/second.
  • the pH of the solution is maintained at 7.6 ⁇ 0.2 by bubbling with N/C0, (95/5) .
  • the entire set-up, including storage containers, is maintained at 37 ⁇ 0.7°C. Effluent solution is collected once a week for a two hour period and analysed for Si and Ca. Analyses are made on a Perkin-Elmer atomic absorption spectrophotometer (AAS) . Further details are given in Environmental Health Perspectives, Volume 102, Supplement 5, October 1994, page 83.
  • the fibres preferably have solubility measured by this test of at least 60 nm/day, more preferably at least 80 or lOOnm/day. More preferably the solubility is at least 120 or 130nm/day. It may even be at least 150 or 160nm/day.
  • the fibres of the invention preferably have T 50 not more than 60, more preferably not more than 50 and in particular not more than 45, especially not more than 40.
  • the fibre products of the invention are made in conventional manner.
  • the composition is usually formed by blending appropriate amounts of naturally occurring raw materials, such as rock and sand materials and recovered waste materials. These include converter slag, other slags, glass, foundry sand, limestone, magnesite, brucite, talc, serpentinite, pyroxenite, apatite, wollastonite, quartz sand, olivine sand, iron ore, dolomite, and MMVF waste.
  • the composition can be converted to a melt in conventional manner, for instance by melting the raw materials in an electric furnace or in a cupola furnace.
  • the melt is preferably produced in a cupola furnace.
  • the melt is formed into fibres by conventional processes comprising pouring the melt into or onto a rapidly spinning fiberising rotor and causing the melt to be flung from the periphery of the rotor as fibres.
  • the rotor may be a spinning cup type of rotor or a rotor having a solid periphery which is usually mounted about a substantial horizontal axis. Rotors of this type can be arranged as a cascade system.
  • the fibres can be formed into MMVF in conventional manner by laying down the fibres in the presence of binder typically in an amount of from 0.5 to 4%, often around 1 to
  • the products may be used for any of the purposes for which MMVF products are known. These include thermal insulation, fire insulation and protection, noise reduction and regulation, horticultural growing media or as free fibres for reinforcement of cement, plastics or other products or as a filler. They may be provided in any of the conventional forms such as slabs or batts, sheets, pipe sections or other shaped products, or may be comminuted to a granular product.
  • raw materials are melted to form a melt which has the composition given below in Table 1.
  • the melt is formed into fibres by means of a cascade rotor system.
  • the fibres are collected as an air laid web and treated to form a product.
  • the melt viscosity at 1400°C is given below for each composition.
  • For each fibre composition the solubility under the in vitro test discussed above is also given.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
EP99932758A 1998-06-30 1999-06-30 Synthetische glasfasern Withdrawn EP1098858A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB9814179.9A GB9814179D0 (en) 1998-06-30 1998-06-30 Man-made vitreous fibres
GB9814179 1998-06-30
PCT/EP1999/004513 WO2000000444A1 (en) 1998-06-30 1999-06-30 Man-made vitreous fibres

Publications (1)

Publication Number Publication Date
EP1098858A1 true EP1098858A1 (de) 2001-05-16

Family

ID=10834705

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99932758A Withdrawn EP1098858A1 (de) 1998-06-30 1999-06-30 Synthetische glasfasern

Country Status (8)

Country Link
EP (1) EP1098858A1 (de)
AU (1) AU4902899A (de)
CA (1) CA2335591A1 (de)
DE (1) DE19840397A1 (de)
GB (1) GB9814179D0 (de)
HU (1) HUP0102949A2 (de)
PL (1) PL345280A1 (de)
WO (1) WO2000000444A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004014344B4 (de) * 2004-03-22 2008-06-19 Saint-Gobain Isover G+H Ag Biologisch abbaubare Glaszusammensetzung und Mineralwolleprodukt hieraus

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2690438A1 (fr) * 1992-04-23 1993-10-29 Saint Gobain Isover Fibres minérales susceptibles de se dissoudre en milieu physiologique.
SK281347B6 (sk) * 1994-02-11 2001-02-12 Rockwool International A/S Výrobok obsahujúci sklenené umelé vlákna
GB9426429D0 (en) * 1994-12-30 1995-03-01 Rockwool Int Man-made vitreous fibres
GB2301351A (en) * 1995-08-16 1996-12-04 Rockwool Int Process for the production of saline-soluble vitreous fibres
FI109294B (sv) * 1997-03-10 2002-06-28 Paroc Group Oy Ab Mineralfiber

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0000444A1 *

Also Published As

Publication number Publication date
DE19840397A1 (de) 2000-01-05
PL345280A1 (en) 2001-12-03
HUP0102949A2 (hu) 2001-11-28
CA2335591A1 (en) 2000-01-06
AU4902899A (en) 2000-01-17
GB9814179D0 (en) 1998-08-26
WO2000000444A1 (en) 2000-01-06

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