Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B30/00—Compositions for artificial stone, not containing binders
  • C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
• • E—FIXED CONSTRUCTIONS
  • E04—BUILDING
  • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
  • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
  • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
  • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls

Definitions

• the present invention relates to porous materials based on dried silica, generally in the form of panels, which are particularly suitable as thermal and/or acoustic insulation materials.
• the invention also relates to a method of obtaining these insulation materials.
• these panels exhibiting a thermal-insulation and/or soundproofing effect are materials based on a porous agglomerate of finely divided particles, essentially containing particles having a low thermal conductivity, such as, for example carbon black, calcium sulfate, calcium carbonate, pyrogenic silica and/or precipitated silica particles in powder form.
• reinforcing fillers such as fibrous materials
• thermally insulating panels are for the thermal insulation of enclosures heated to high temperature, such as industrial thermal enclosures (furnaces or ovens for example) or thermal enclosures of the household type (such as pyrolitic ovens in particular).
• enclosures heated to high temperature such as industrial thermal enclosures (furnaces or ovens for example) or thermal enclosures of the household type (such as pyrolitic ovens in particular).
• thermal insulation panels within this context is the manufacture of fire doors or site walls intended in particular for limiting the propagation of the onset of fires or for bringing fires under control.
• the material is in general subjected to temperatures that can vary widely, such as for example to temperature cycles in which the temperature rises and falls within a furnace or oven.
• temperatures that can vary widely, such as for example to temperature cycles in which the temperature rises and falls within a furnace or oven.
• These thermal variations have a tendency to induce expansion and contraction phenomena within the material, which may be unacceptable in certain applications and also usually result in high mechanical stresses liable to weaken the structure of the material over the relatively long term.
• incorporating reinforcing fillers limits these phenomena, but this does not always prove to be sufficient for inhibiting them and for ensuring satisfactory mechanical integrity of the material.
• opacifying agents such as for example titanium dioxide particles. These opacifying agents reflect, absorb and/or disperse at least part of the infrared radiation and thus consolidate the thermal barrier effect of the material. Even so, it turns out that the mere presence of these opacifying agents does not always make it possible to obtain optimum thermal insulation properties.
• a conventional method for preparing the aforementioned thermal and/or acoustic insulation panels consists in carrying out a dry compacting operation of their constituents, namely by applying pressure to the particles of low thermal conductivity, generally in combination with reinforcing fillers, and optionally opacifying agents.
• This method is in general carried out by introducing these constituents in the form of a blend of finely divided particles and/or powders in a porous envelope, for example a bag or a cushion made of glass fabric and then applying a high pressure (typically of about 10 bar or more) to said envelope, in order to bond the particles together, so as to obtain a compressed material having a certain mechanical integrity.
• the panels obtained according to this dry compacting method usually have insufficient physical and/or mechanical properties.
• the thermal and acoustic insulation properties of the materials often prove to be bad, in particular when the low thermal conductivity particles involved in their structure are carbon black, calcium sulfate or calcium carbonate particles.
• More acceptable insulation properties may be obtained by using silica particles.
• materials having insufficient mechanical properties are obtained, said materials being in particular friable and inclined to cracking.
• Patent EP 0 594 469 describes a method of preparing insulating panels based on dried silica, which consists in drying an aqueous composition obtained by blending a pulverized cake of precipitated silica to which at least one reinforcing filler, and optionally an opacifying agent, have been added.
• the materials obtained according to the method of EP 0 594 469 exhibit satisfactory mechanical integrity, combined with thermal and acoustic properties at least similar to those of the materials obtained by dry compacting, and usually superior to them. In this regard, it seems reasonable to suppose that the operation of drying an aqueous slurry instead of a dry compacting operation makes it especially possible to increase the pore volume of the material obtained in fine.
• the method of EP 0 594 469 also proves to be economically more advantageous than dry compacting, especially insofar as it obviates the expensive and burdensome phases of blending powders and compacting them at high pressure.
• the aqueous composition which undergoes the drying operation is in general a slurry with a solids content of at least 10%, which is fluidized (disintegrated) before being introduced into a mold, and then dried.
• the inventors have discovered that it is possible to further improve the properties of the insulation materials which are obtained by drying aqueous compositions based on precipitated silica particles, by carrying out the drying operation on a precompacted aqueous composition, e.g. a cake obtained by filtering a precipitated silica dispersion in a filter press.
• a precompacted aqueous composition e.g. a cake obtained by filtering a precipitated silica dispersion in a filter press.
• the inventors have surprisingly discovered that it is possible to improve the method of EP 0 594 469, especially by avoiding one of the steps of this method, thereby making it possible to produce more advantageous materials by means of a less expensive method.
• the use of a mold is no longer necessary for the drying step insofar as the compacted cake is already formed in the filter press. This further reduces the production costs of the material.
• the materials obtained by the inventors are moreover particularly suitable for use in a vacuum, in which they especially exhibit good mechanical integrity and useful thermal insulation properties.
• the present invention aims to provide a method of preparing insulating materials of the dried-silica panel type having mechanical integrity and thermal and/or acoustic insulation properties at least similar, and preferably superior, to those of currently known silica panels, and to attend this aim with a lower production cost than with the methods of the prior art.
• An object of the invention is further to provide novel materials based on dried silica that are suitable for thermal and/or acoustic insulation, and preferably suitable for thermal insulation at high temperature.
• the aim of the invention is in particular to provide such materials in the form of dried-silica panels having in particular sufficient mechanical integrity to allow them to be handled.
• the aim of the invention is also specifically to provide such materials that are suitable for vacuum processing, especially in order to produce vacuum thermal insulation.
• the subject of the present invention is a method of preparing a thermal and/or acoustic insulation material based on dried precipitated silica, comprising the steps consisting in:
• thermo and/or acoustic insulation material is understood to mean, within the context of the present invention, a porous solid having sufficient mechanical strength for it to be able to be handled, and possessing absorption, reflection and/or dispersion properties for thermal radiation and/or acoustic waves.
• the thermal and/or acoustic insulation material prepared according to the invention takes the form of a particulate panel, preferably of rectangular or square shape.
• the drying of step (B) consists in substantially removing the water contained in the compacted cake obtained from step (A), optionally after demolding the compacted cake obtained in the filter press.
• step (B) generally results essentially in the formation of a one-piece solid, the shape of which is determined by the filter press used in step (A), which acts as a mold for the compacted cake produced.
• step (A) when it is desired to obtain an insulation panel of given shape, it is usually advantageous to carry out step (A) within a filter press having said shape, for example in a filter press having a rectangular or square shape.
• the compacted cake obtained in step (A) may, in certain cases, be demolded from the filter press and then cut up into the desired shape, prior to the drying of step (B).
• the cutting-up operation should in particular be carried out with the least possible vibration.
• step (A) whose purpose is to form a compacted filter cake.
• the work carried out by the inventors seems to indicate that, the greater the compacting of the cake produced in step (A), the greater the reduction observed in the size of the pores present in the material obtained after the drying of step (B), thereby improving the insulation properties.
• excessive compacting results, on the contrary, in a material having a low pore volume, which is prejudicial to the insulation properties. Therefore, in the general case, it is necessary to carry out the compacting of the cake from step (A) under moderate pressure.
• the filtration in the filter press of step (A) preferably includes a compacting operation with a pressure of between 2 and 10 bar (that is to say between 2 ⁇ 10 5 Pa and 10 ⁇ 10 5 Pa).
• the pressure employed is 3 bar or higher, and more preferably 4 bar or higher.
• this pressure in particular to minimize the reduction in pore volume of the material obtained in fine, it often proves advantageous for this pressure to be 8 bar or less, preferably 7 bar or less, and more preferably less than 6 bar.
• the pressure at which the compacting of step (A) is carried out is thus between 2 and 7 bar and preferably between 4.5 and 5.5 bar (typically around 5 bar).
• the compacted filter cake obtained after step (A) has a solids content of at least 10% by weight and preferably at least 15% by weight, this content generally remaining less than 35% by weight. Usually, it is preferred for this solids content to be between 20 and 30% (typically around 25%).
• the pressure filtration of step (A) is generally carried out for a time of at least 10 minutes, typically between 10 and 40 minutes, and preferably for at least 20 minutes, especially so as to establish the optimum porosity within the material.
• step (A) comprises two successive steps, namely:
• this step is in general carried out at room temperature (typically at a temperature between 10 and 30° C.) However, according to certain methods of implementation, higher temperatures may be envisaged, (especially temperatures between 30 and 80° C.), for example in order to increase the filtration rate.
• the aqueous precipitated-silica-based dispersion D subjected to the filtration of step (A) in a filter press may in general be any dispersion based on precipitated silica particles.
• the term “precipitated silica” denotes, within the context of the present description, any silica obtained by the reaction of a silicate with an acid, according to any method of preparation, especially by the addition of an acid to a silicate stock, or else by simultaneous, total or partial, addition of acid and silicate to a water or silicate stock.
• the suspension D is a silica slurry such as that obtained after such reactions, to which various additives may optionally be added.
• the precipitated silica present in the aqueous dispersion D is a precipitated silica which, once dried, has a BET specific surface area of between 80 and 400 m 2 /g, and preferably between 100 and 350 m 2 /g and a CETAB specific surface area of between 80 and 350 m 2 /g, and preferably between 100 and 250 m 2 /g.
• precipitated silicas that are particularly suitable for implementing the method of the invention, mention may particularly be made of the precipitated silicas obtained by the methods described for example in EP 0 520 862, WO 95/09127, WO 95/09128, or WO 03/016215.
• the initial solids content of the suspension D that is subjected to the pressure filtration of step (A) may vary quite widely. However, it is preferable for this initial solids content before filtration to be between 5 and 30%, and preferably between 15 and 25% by weight.
• the precipitated silica in the aqueous dispersion D is the predominant solid compound. Thus, it is preferable for the precipitated silica in the dispersion D to be present in an amount of at least 50% by weight, preferably at least 75% by weight relative to the total mass of solids of the dispersion D.
• the aqueous dispersion D used in step (A) contains, in addition to the precipitated silica, a reinforcing filler.
• this filler is intended to increase the mechanical integrity of the insulation panel obtained by the method.
• this reinforcing filler preferably contains reinforcing fibers chosen from the group formed by aluminum silicate fibers, alumina fibers, mineral wool fibers, glass fibers, quartz fibers, ceramic fibers, polymer fibers and cellulose fibers, said reinforcing fibers preferably being glass fibers or polymer fibers, such as polyamide fibers.
• the (silica/reinforcing filler) mass ratio in the aqueous dispersion D of step (A) is between 75/25 and 99/1, and preferably between 85/15 and 98/2.
• the aqueous dispersion D used in step (A) may contain, in addition to precipitated silica and an optional reinforcing filler, an opacifying agent, namely a compound capable of reflecting absorbing and/or dispersing at least part of the infrared radiation.
• an opacifying agent acting as an infrared barrier is advantageously chosen from the group consisting of chromium oxide, zirconium oxide, iron oxide, titanium dioxide, manganese dioxide, ilmenite, quartz powder, silicon carbide, boron carbide, tantalum carbide, carbon black and graphite, in general in particulate form.
• the titanium dioxide and ore particles that it comprises, in particular the ilmenite particles, constitute particularly suitable opacifying agents within the context of the present invention.
• the (silica/opacifying agent) mass ratio within the aqueous dispersion D is between 50/50 and 99/1, and preferably between 70/30 and 90/10.
• step (A) consists in carrying out a pressure filtration operation on this dispersion, so as to obtain a compacted cake whose solid phase has substantially the same composition as the solid phase of the suspension D.
• step (A) may prove beneficial for step (A) to include one or more washing operations (using water or solvents).
• the washing operation(s) must however be carried out taking care not to obtain a pulverized cake after step (A).
• step (B) of the method of the invention must be carried out on a filter cake in the compacted state.
• washing steps it is in general preferable that they be carried out in the filter press, and advantageously under pressure, so as to obtain a properly compacted cake prior to drying.
• the drying step (B) of the method of the present invention generally consists in substantially removing the water present in the compacted cake obtained from step (A), in general so as to obtain a water content in the material of 15% or less, and typically between 1 and 10% by weight. In general, this drying is carried out slowly, especially so as to optimize the cohesion of the various particles and to avoid the formation of cracks, which would be liable to affect the insulating properties of the material, or even its mechanical strength.
• step (B) may be carried out by leaving the compacted cake obtained after step (A) in the filter press used for the filtration.
• the compacted cake obtained after step (A) is in general sufficiently compacted for it to be possible to demold it from the filter press without appreciably affecting its compacted character.
• step (B) When it is desired to demold the compacted cake from step (A) prior to the drying of step (B), it is in general advantageous to coat the internal surface of the filter press with a mold-release agent such as, for example, an organic oil or a silicone oil, prior to the pressure filtration of step (A).
• a mold-release agent such as, for example, an organic oil or a silicone oil
• step (B) of the method of the invention is carried out by leaving the compacted filter cake obtained after step (A) to dry at room temperature, namely at a temperature between 10 and 30° C., preferably between 15 and 25° C.
• room temperature namely at a temperature between 10 and 30° C., preferably between 15 and 25° C.
• the evaporation time may vary widely according to this first embodiment. However, usually a drying operation lasts around 10 to 20 days, or even a shorter time.
• step (B) is carried out by subjecting the compacted filter cake as obtained after step (A) to a progressive temperature rise, generally from room temperature (typically 20° C.) up to a temperature of at least 100° C., or even up to a temperature of at least 200° C., with the slowest possible rate of temperature rise, preferably less than 2° per minute, and typically not exceeding 0.5° C. per minute.
• a progressive temperature rise it proves to be advantageous to hold the temperature at one, two or three intermediate temperature levels.
• step (B) may be carried out under the drying conditions described in Patent EP 0 594 469.
• the subject of the present invention is porous thermal and/or acoustic insulation materials based on dried precipitated silica, which can be obtained by the method described above. These materials usually take the form of panels, generally of rectangular or square shape.
• the materials according to the present invention have a porous structure with a small pore size.
• the “pore size” referred to here is the pore size as determined using the mercury porosimetry method, for example by means of a porosimeter of the Micromeritics Autopore III 9420 type.
• the porous specimens tested are prepared as follows: the specimen is dried for two hours in an oven at 200° C.
• the pore diameters are calculated by the Washburn equation with a contact angle ⁇ of 140° and a surface tension ⁇ of 484 N/m (or dynes/cm).
• the pore volume of the pores smaller in size than 1000 nm represents at least 40%, and usually at least 50%, of the total pore volume of the material.
• the pore volume of the pores smaller in size than 1000 nm represents at least 60%, or even at least 70%, of the total pore volume.
• the pores smaller in size than 100 nm are predominant.
• mercury porosimetry shows that the pore volume of the pores smaller in size than 100 nm represents at least 50%, in general at least 60%, and advantageously at least 70% of the pore volume of pores smaller in size than 1000 nm.
• this proportion of pores smaller in size than 100 nm is higher the greater the pressure at which the filtration of step (A) is carried out.
• a material according to the present invention generally possesses a relatively high total pore volume.
• the term “pore volume” is understood here to mean the volume of the accessible pores of the material, as determined by the aforementioned mercury porosimetry method. This total pore volume is generally between 1 and 5 cm 3 /g (between 1 and 5 ml/g), and usually between 1.2 and 4 cm 3 /g, this total pore volume preferably being greater than 1.5 cm 3 /g, advantageously at least 2 cm 3 /g and even at least 2.5 cm 3 /g.
• the pore volume of the pores smaller in size than 100 nm is itself at least 1 cm 3 /g, usually at least 1.1 cm 3 /g and preferably at least 1 cm 3 /g.
• Materials having large pore volumes are in general obtained when the pressure at which the filtration of step (A) is carried out is relatively low, typically when this pressure is around 5 bar or less (for example between 2 and 5.5 bar).
• step (A) it is usually necessary to carry out step (A) at a high pressure, advantageously at least equal to 3 bar, preferably 4 bar, especially so as to obtain the highest possible mechanical strength of the material.
• an insulation material according to the invention generally has a composition extremely similar, and usually identical, to that of the solid phase of the aqueous dispersion D.
• a material according to the invention consists predominantly of dried precipitated silica, that is to say with a content of at least 50% by weight, preferably at least 75% by weight and advantageously at least 80% by weight relative to the total weight of the material.
• a material according to the invention may also include other elements than dried silica, and in particular additives such as a reinforcing filler and/or an opacifying agent.
• a material according to the invention is a material obtained from a dispersion D comprising, in addition to precipitated silica, a reinforcing filler.
• a material comprises:
• a material according to this embodiment is particularly suitable as a thermal and acoustic insulation material for walls or ceilings of buildings or dwellings. Its thermal insulation properties also make it suitable as a fire-stop material.
• a material according to the invention is a material obtained from a dispersion D comprising, in addition to precipitated silica, an opacifying agent, and optionally a reinforcing filler.
• such a material comprises:
• a material according to this specific embodiment is particularly intended for producing a high-temperature thermal insulation, in particular for the insulation of enclosures heated to high temperatures, or as constituent materials of fire-stop barriers. These materials are also suitable for the more usual uses of thermal and acoustic insulation, such as the insulation of walls and ceilings.
• the materials obtained according to the method of the invention prove to be useful as thermal and/or acoustic insulation material, and in particular for thermal insulation under reduced pressure.
• a silica cake was produced according to the method described in example 1 of EP 520 862.
• the cake as obtained after the filtration step in a filter press, which had a solids content of 21%, was diluted with water so as to obtain a silica suspension or slurry having a solids content of 13.5% by weight, and the pH of this silica suspension was increased to 5 by the addition of sulfuric acid (80 g/l aqueous solution).
• the mixture obtained was then filtered in the filter press used in Example 1 above (filter press with an inside diameter of 7 cm). A compacting pressure of 5 bar was applied, after which a compacted cake having a solids content of 27% by weight was obtained. The formed cake thus obtained was demolded and left to dry at room temperature as in the previous example. After 10 days, a dried cake with a solids content of 95% was obtained. Thus, a silica panel having a good mechanical strength and a density of 0.4 was obtained.
• the silica panel obtained had a total pore volume of 3.3 ml/g, with a pore volume of pores smaller in size than 100 nm of 1.2 ml/g.
• Thermal conductivity measurements were carried out using a TC-meter on the two silica panels of Examples 1 and 2.
• the principle used was that called the “thermal shock probe”, which is similar to the method used according to the ISO 8814-1 standard.
• thermal conductivity coefficient of the silica panels of Examples 1 and 2 was measured at various pressures in the following manner: a thermal probe was placed within the material to be characterized.
• the thermal equilibrium of the material was disturbed by generating a heat flux by means of the heating element of the probe.

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• 2003
  • 2003-06-30 FR FR0307903A patent/FR2856680B1/fr not_active Expired - Fee Related
• 2004
  • 2004-06-29 EP EP04767513A patent/EP1641726B1/fr not_active Expired - Lifetime
  • 2004-06-29 ES ES04767513T patent/ES2307049T3/es not_active Expired - Lifetime
  • 2004-06-29 DE DE602004013780T patent/DE602004013780D1/de not_active Expired - Lifetime
  • 2004-06-29 AT AT04767513T patent/ATE395311T1/de not_active IP Right Cessation
  • 2004-06-29 WO PCT/FR2004/001669 patent/WO2005003057A2/fr active IP Right Grant
  • 2004-06-29 US US10/562,908 patent/US20070181845A1/en not_active Abandoned
  • 2004-06-29 JP JP2006516338A patent/JP4435160B2/ja not_active Expired - Fee Related
• 2015
  • 2015-08-24 US US14/834,044 patent/US9903109B2/en not_active Expired - Fee Related

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