The present invention relates to a composite panel to cellular thermosetting matrix, a method of manufacturing this panel structure and a coating of a wall which is formed of an assembly of such panels and gives the wall thermally insulated vis-à screw cryogenic fluids and / or protection against ie fire and the flames and / or sealing such fluids. The invention applies in particular to such a structure for coating a platform, a bridge or a hull of a floating production unit liquefied gas offshore, and more generally any other application for example in the aeronautical field requesting at least one of the three aforementioned properties of thermal insulation, protection and waterproofing.

In known manner, it is sought to protect from leakage or spillage of cryogenic liquid (ie of liquefied gases having a temperature in the liquid state is less than -150 ° C, such as liquefied petroleum gas called LPG, or ie natural gas! liquefied) decks and hulls of floating production offshore liquefied gases, particularly during pumping, processing such as separation, liquefaction, storage and transhipment applied to these liquids. Indeed, we know that the cryogenic liquid flows can damage structures typically used in steel decks and hulls of ships or platforms by brittle fracture. C '

It also seeks to giving substrates such bridges and shells satisfactory fire resistance, including a allumabiitté

reduced to ia flame propagation resistance, reduced smoke emissivity and thermal insulation (to prevent a critical heating of the substrates).

It is thus known to use protective coating structures in the form of an assembly of panels forming paving on these substrates, these panels being constituted by exampIe:

- a cellular foam composition such syntactic based on a polymer matrix and injected hollow microspheres, with the major disadvantages sealing cryogenic fluids and a mechanical resistance both insufficient,

- a compact plastic composition of thermosetting type, with the disadvantages binding geometric modularity, a weight and a too high cost, or

- a fiber-reinforced composite cellular thermosetting matrix, as described in particular fe paper commented below.

The document WO-A1 -2014/009381 has a composite panel foamed thermosetting matrix comprising a support made of natural fibers impregnated with this matrix is ​​based on a water-based resin and a blowing agent. The support is formed of a felt which is shown as preferably comprising staple fibers basalt, provided that Îa description tunic exampIe of manufactured panel mentions the use of short fibers but not unlike continuous type son " BCF "(ie" was based Continuous filaments "). According to this document, it is necessarily aiguiileté felt on both surfaces thereof by the provision of additional thermoplastic fiber poiyéthylène.

A major drawback of the presented panel in this document resides in that fiber intake in poiyéthylène which is required to confer a satisfactory integrity felt for weights thereof specifically between 480 and 780 g / m *.

However, it is likely that this contribution fiber poiyéthylène while needling surface Felt does not significantly improve its mechanical properties, instead being able to generate a lack of homogeneity in you felt resulting in its surface mass locally variable which, in fields such as aeronautics, problem.

In addition, twisted heating the fiber holder by means of a hot press at the third step of crosslinking and expansion of the thermosetting resin described in this document, one uses a heating temperature of between 90 ° and 15D C and preferably between 135 and 145 ° C to allow both an activation of the blowing agent and ia crosslinking of the resin. However, the heating temperature may negatively interfere with the polyethylene fibers made during prior i'aiguilietage, since it is in ia usual range of the polyethylene melting temperature (85 to 140 ° C) which can render these totally useless poiyèthylène fibers and result in accumulations of molten poiyèthylène in certain areas of the panel.

Besides the aforementioned drawbacks panel according to this document that are directly related to the support by these I'aiguilietage fsbres of poiyèthylène, it appears that the mechanical properties of the tested panel have been improved as relatively, given the thickness high obtained for the panel in relation to its density.

An object of the present invention is to provide a composite panel è cellular thermosetting matrix, the panel comprising at least one support which comprises short fibers and basalt nonwoven which is impregnated by said matrix, which overcomes the aforementioned drawbacks,

For this purpose, a panel Seion the invention is such that said at least one support comprises a plurality of nonwoven superposed in a superposition of thickness, said nonwoven comprising each said short fibers basalt and being needled into said thickness without filler thermoplastic fibers.

By "nonwoven" is meant in a known manner in the present description a processed sheet composed of a web, a web, a felt or a mat of fibers oriented in a particular direction or randomly, bonded by friction and / or cohesion and / or adhesion, excluding paper and products obtained by weaving, knitting, tufting or seaming.

By nonwoven "needled" means so also known their mechanical consolidation by needling technique, which has the effect of creating bridges of vertical fibers between the different sheets to keep them together. For this reason, the aiguilietage can apply only long enough fibers, typically of ' at least 30 mm and usually at least 40 mm, as is the case of short fibers of basalt used in these nonwovens.

Note that the panel of the invention is thus characterized by stacking a plurality of nonwoven layers, such as for example felts, which comprise short fibers basalt preferably a majority or exclusively (Le. in a mass fraction greater than 60% and still pius préférentleilement greater than 90%, optionally 100%).

According to another characteristic of the invention, short fibers lesdiîes basalt included in or constituting each non-woven fabric may have an average diameter between 13 microns and 16 prn and a mean length of between 30 mm and 60 mm and preferably between 35 mm and 45 mm. provided that such short fibers basalt used in the present invention can be stored to the limit in ia category "TSF" (Thin Stapîe was based Fibers "in English), although their average diameter is slightly greater than that of the fibers" TBF " commercially available which is usually between 5 .mu.m and 12 .mu.m.

Note that these basalt fiber type "TBF" used in the nonwovens of the present invention particularly have the advantage of withstanding temperatures up to 1040 ° C without being altered.

Also note that can not be used as short fibers of basalt in the nonwovens of a panel according to the invention:

- basaite of the fibers of the type "BCF" ( "was based Continuous Fibers" in English), ie continuous fibers of mean diameter usually between 6 microns and 21 microns and very high average length

typically between 40 km and 60 km, the fact that these fibers "BCF" does not impart sufficient mechanical strength to the nonwoven superposed and require, as explained in aforesaid ie WO-A1 -2014/009381, the supply of needling fibers polyéthyiéne or

- basalt fibers type "STBF" ( "Super Thin was based

Fibers "in English) in diameter usually between 1 and PRN 3 microns and typically around average length of 50 mm, the fact that these fibers of very small diameter not cling together sufficiently to obtain a non-ttssé type felt and are also harmful to health,

the structural feature of being needled together and depth through this stack and without the addition of any thermoplastic fiber IORS needling It is further noted that these nonwovens according to the invention, unlike the above-mentioned document WO-A1 -2014/009381 which teaches a needling the two surfaces of a single felt with addition of thermoplastic fibers in polyethylene. This aiguifietage long nonwovens according to the invention without the addition of thermoplastic material (eg without the addition of polyolefin such as polyéthyiéne or any other thermoplastic polymer) allows to obtain a satisfactory mechanical strength of nonwovens by connecting between them while overcoming the aforementioned drawback of this document inherent in the use of fibers of

Advantageously, said superposed nonwovens several may comprise at least three and preferably four so-called nonwovens.

According to a first embodiment of the invention, these superposed nonwovens are needled with intake of continuous basalt fibers.

In accordance with this first embodiment, said basalt continuous fibers may form parallel chain son inserted into said non-woven superposed, said warp FIIs being in pairs spaced apart from ' a distance of preferably between 10 cm and 40 cm and, even more preferably, between 15 cm and 25 cm.

Advantageously, these basalt continuous fibers may have a linear density between 100 tex and 300 tex, preferably between 180 and 230 tex, and preferably correspond to the name "BCF"

Note that these basalt continuous fibers can improve strength of said support ia ie in direction of the length (Le. The direction of the warp son).

AIso accordance with this first embodiment Power, the said superposed nonwovens may each be formed (ie exclusively} of these short fibers basalt and these continuous fibers basalt, and may each have a basis weight between 480 and 2000 g / rn 2 .

According to a second embodiment of the ' invention, superposed nonwovens Iesdits each have a basis weight greater than 1000 g / m 2 and are aiguiiletés without providing no fibers.

In accordance with this second embodiment, superposed nonwovens iesdits may thus each be made (ie, exclusively) of said short fibers basalt.

Advantageously, said at least one support impregnated with said thermosetting matrix may comprise Iesdits nonwoven superposed in a mass fraction between 15 and 25% and said matrix in a weight fraction of between 75 and 85%.

Also advantageously, the thermosetting matrix may comprise (percentages by weight):

- between 50 and 65% of a water-based resin selected from the group consisting of melamine-formaldehyde resins, phenolic resins and wood adhesives, preferably melamine-formaldehyde;

- between 3 and 15% of an agent ' expansion for the formation of open cells which preferably comprises isobutane (for pressing temperatures below 150 "C) or isopentane (for pressing temperatures above 150 ° C);

~ Between 0.5 and 2% of a catalyst preferably comprising the amine hydrochloride;

- between 30 and 45% of an aqueous soivant such as water; and

- between 0 and 3% of optional additives such as shredded carbon or graphite, for example.

According to another characteristic of the invention, said non-woven superposed and impregnated with said thermosetting matrix may have a density between 60 kg / m 3 and 1200 kg / m 3 and a thickness of between 5 mm and 30 mm.

Advantageously, said panel may further comprise:

- at least an aluminum foil located outside said superposed nonwovens said at least one carrier, for example located between said two supports each consist of said superposed nonwovens, and / or

- an outer layer forming a panel of the protective coating which is selected from the group consisting of rubbers, thermoplastic elastomers, epoxy paints and polyurethanes.

Note that this outer layer is for example intended to form a top layer of a coating structure of a wall or substrate according to the invention defining the outer surface of a floor, platform, deck or hull which can evolve operators.

Advantageously, said panel may have:

* A thermal conductivity at 25 ° C less than or equal to 50 mW m "1 K " 1 (preferably 35 mW.m '1 K ' '), in particular giving it a good thermal insulation to the cryogenic fluid so that the temperature of the underlying substrate is not lower than -60 ° C, and / or

- a seal at cryogenic fluids to avoid any contact of these fluids with the underlying substrate, and / or

- passive fire resistance include:

* A CFL-S1 class altumabilité, according to the Nf EN 13501-1,

* Resistance to flame spread less than 25, measured according to ASTM E84,

* An indication of emissivity of flue gas less than 130, measured according to ASTM E84, and

* Thermal insulation fire ensuring a temperature not underlying substrate higher than 427 ° C.

the panels of the invention will be appreciated that present the advantage of being transparent to microwave, including the specific water frequency (between 1000 and 1100 MHz), and being easily repairable.

A coating structure according to the invention of ' a wall to impart to said wall a thermal insulation vis-à-vis of cryogenic fluids and / or protection against heat and flames and / or a seal to these fluids, structure being particularly suitable for coating a platform, a deck or hull of a floating production unit offshore liquefied gas, is such that the structure of said panels comprises an assembly intended to be fixed to the wall, the panels being connected together by tight joining means preferably comprising composite short fiber based basalt cords impregnated with a thermosetting matrix cell Identical or different from that of the panels.

Note that the coating structures according to the invention may relate to the coating of any wall or underlying substrate, that this wall is for example horizontal (the structure then forms a paving formed by an assembly of slabs for example polygonal) vertical or other, and that these structures can for example protect the walls such as walls or partitions against fires. Alternatively, these structures can protect buildings, industrial equipment (including pipes or thermally insulated cryogenic tanks), and ground vehicles, rail, sea, river, air or space.

A manufacturing method according to the invention a said panel of the invention is such that it comprises the following successive steps:

a) aiguiiletage said superposed nonwovens said at least one carrier in said superimposing thickness without the addition of thermoplastic fibers, preferably with addition of continuous fibers of basalt, b) impregnation with said matrix nonwovens aiguiiietés, c) calendering said nonwovens impregnated,

d) drying said non-woven impregnated and calendered, and then

e) pressing said non-woven impregnated, caiandrés and dried between heated platens controlled spacing.

Other features, advantages and details of the present invention rassortiront on reading ia following description of several embodiments of the invention, given for illustrative and non-limiting, IA description being made with reference to the accompanying drawings, in which :

Figure 1 is a partial cross section schematic view of a holder included in a panel according to an example of the invention conforms to said first mode, showing the implementation of needlepunching applied to the support prior to impregnation with the thermosetting matrix ,

Figure 2 is a partial schematic view in cross section of the support Figure 1 ia needled and impregnated with the matrix,

Figure 3 is a partial perspective view of a panel according to the invention showing a grooved longitudinal edge of the panel for receiving a joining means with another panel,

Figure 4 is a partial perspective view of detail showing ia edge of the panel assembly of Figure 3 to that of another panel by interposing the joining means, and

Figure 5 is a partial top view and enlarged view of the assembly of Figure 4.

The carrier 1 according to the example of the invention shown in process in Figure 1 comprises four non-woven fabrics 2, 3, 4, 5 bunk for example of felt which, illustrated prior to needling tools 6 and 7 provided with needles 6a and 7a, are predominantly or exclusively made up of staple fibers basalt 2a, 3a, 4a, 5a substantially type "TBF". Preferably, the fibers 2a, 3a, 4a, 5a can advantageously have an average diameter of about 13 pm and an average length of about 40 mm.

In the example of Figure 1, the fibers 2a, 3a, 4a, 5a are shown purely schematically, it being understood that a more or less random orientation of fibers 2a-5a is also conceivable for each of the non-woven 2 -5.

After aiguiiieiage long nonwoven 2-5 obtained by the reciprocating movements of outiis 6 and 7 in the direction of double arrows A so that ies needles 6a and 7a through each totaie the thickness of non-woven overlay 2- 5 with addition, according to this first mode [invention, long fibers (substantially continuous ie) class basalt "BCF" to form warp son 8, there was obtained partially ie visible needle carrier in Figure 1 and so completed in Figure 2 with insertion continuous chain son 8 basalt (only one is visible in these figures) following spacings son chain 8 consecutive between 10 cm and 40 cm and advantageously about 20 cm . As a filler type fibers "BCF" used for this aiguilietage,

The basis weight or grammage of the multilayer nonwoven needled 2-5 ies via continuous fiber 8 is advantageously between 480 and 1000 g / m 2 including 780 g / m 2 , it being specified that in this embodiment of Figure 2 ies nonwoven 2-5 superposed on a thickness e consist of basalt fibers, the fibers comprising short 2a-5a in a majority proportion and continuous ies son S in a minority proportion (by mass).

As indicated previously in the presentation-General of the present invention, it is noted that it is alternatively possible to achieve this aiguilietage nonwoven 2-5 without the addition of fibers, said nonwoven being 2-5 then only consist of only short fibers 2a-5a basalt.

Following this aiguilietage, nonwovens 2-5 was impregnated with a thermosetting matrix 9th base (ie mainly composed by weight) of a thermosetting resin in an aqueous base preferably consists of a copolymer of melamine-formaldehyde (with a rate

-1

formaidéhydes mass of the order of 0,2,10% only).

Table 1 below shows an example of test formulation ie to support 1 consisting of non-woven needled 2-5 and for the composition of the thermosetting matrix 9 impregnating this support 1.

Table 1:

To manufacture composite panels 10 according to the invention from nonwoven support 1 impregnated with this matrix 9, there is proceeded as follows according to a free embodiment of the invention.

In a first step, a calendering method of the support 1 IA impregnated matrix 9 to control the relative proportion between the support 1 and the die 9.

In a second step, carried out the drying of the support impregnated with 1 ia matrix 9 and calendered as follows:

* Evaporation of a portion of the water of the medium 1 for 2 hours;

* Condensation of evaporated water for 2 hours;

* * Evacuation continuously from the condensed water; then

" Repeating these two cycles of evaporation and condensation for a period ranging from 24 hours to 48 hours.

In a third step, a method for pressing the support 1 in the dry state between two heating plates with controlled spacing as follows:

* Cycle of 8 minutes at 120 ° C with a force of 300 kN on piateaux;

* Cycle of 30 seconds at 0 kN (decompression);

* 7-minute cycle at 120 ° C with a force of 300 kN on the trays; then

* Product cooling on a flat surface during

30 minutes.

Note that it is conceivable, within the framework of the manufacturing process of a panel according to 10 (invention, pressing:

- one or more nonwoven substrates 1 together in a single cycle, or alternatively

- n carriers 1 one after the other (in n cycles), with n an integer inclusive between 2 and 5 (in this case, the different supports 1 may have the same thickness or not).

Composite panels there was thus obtained 10 according to the invention which were each formed of a rectangular Daile as iiiustré to Figures 3 to 5, it being understood that one could alternatively obtain panels 10 of square geometry, or otherwise polygonal. The highest areas obtained for these panels 10 of the invention, which were limited to the surfaces of the presses used, were in such embodiments between 0.5 m 2 and 6 m 2 . In addition, these panels 10 each had a density which was between 60 kg / m 3 and 1200 kg / m 3 and which can vary or not ia surface of each panel 10, for a panel thickness 10 between 5 mm and 30 mm.

The panels 10 the above tests was subjected, including as a result of thermal conductivity at 25 ° C less than or brightens 35 mW.m -1 K - 1 a sealing cryogenic fluids and a passive resistance satisfactory fire (as measured by said ailumabiiité, said flame propagation resistance, said emissivity index fumes and said thermal insulation to fire).

As illustrated in Figures 3 to 5 was formed in each of the two longitudinal edges 1 1 There each panel 10 a longitudinal groove 12 receiving a connecting cord composite 13 sealed to obtain a coating of a wall structure 20 according to the invention.

Each cord 13 was based on the same short fibers basalt than 2a ~ 5a nonwoven 2-5 impregnated with the same thermosetting cell matrix 9 that the matrix used to impregnate the nonwoven 2-5 (being clarified that alternatively can be used a composite cord cell 13 based on a carrier and / or other impregnating die (s) as those of each panel 10).

In the example of Figures 3 to 5, each groove 12 has a cross section asymmetrical U, ie delimited by an edge 14 (lower in the figures) wider than the other edge 15 (upper in the figures), so that upon abutment of two panels 10 in one plane by the two edges of the grooves 12 positioned opposite each other, the lower edges 14 are substantially larger in abutment one against the other and the upper edges of narrower 15 are spaced from one another. Each junction bead 13 and in cross section substantially a T-shape (ie

Note that it is possible to obtain a coating structure 20 modular variable area which is adapted to that of the wall underlying protect.

CLAIMS

1) A composite panel (10) to cellular thermosetting matrix (9), the panel comprising at least one support (1) comprises short fibers nonwoven basalt (2a, 3a, 4a, 5a) and which is impregnated by said matrix characterized in that said at least one support comprises a plurality of non-woven (2, 3, 4, 5) superposed in a superposition of thickness (e), said nonwoven comprising each said short fibers basalt and being needled into said thickness without the addition of thermoplastic fibers.

2) A panel (10) according to claim 1, characterized in that said plurality of non-woven (2, 3, 4, 5) superposed comprise at least three and preferably four so-called nonwovens.

3) A panel (10) according to claim 1 or 2, characterized in that said non-woven (2, 3, 4, 5) are needled with bunk intake basalt continuous fiber strands (8).

4) A panel (10) according to claim 3, characterized in that said basalt continuous fibers (8) form parallel warp son inserted into said non-woven (2, 3, 4, 5) superposed, said warp son being in pairs spaced apart a distance of preferably between 10 cm and 40 cm.

5) A panel (10) according to claim 4, characterized in that said basalt continuous fibers (8) have a linear density between 100 tex and 300 tex, and preferably correspond to the name "BCF".

6) A panel (10) according to one of claims 3 to 5, characterized in that said non-woven (2, 3, 4, 5) arranged one above each consist of said short fibers basaite (2a, 3a, 4a, 5a) and said basalt continuous fiber strands (8).

7} panel (10) according to one of the preceding claims, characterized in that nonwovens iesdits (2. 3, 4, 5) arranged one above each have a basis weight of 480 g / m 2 and 2000 g / m 2 .

8) A panel (10) as claimed ia claim 1 or 2, characterized in that nonwovens iesdits (2, 3, 4, 5 bunk} each have a basis weight greater than 1000 g / m 2 and are needled without the addition of no fibers

9} A panel (10) as claimed ia claim 8, characterized in that nonwovens iesdits (2, 3, 4, 5) arranged one above each consist of said short fibers basaite (2a, 3a, 4a, 5a).

10) Panel (10) according to one of the preceding claims, characterized in that iesdites short fibers basaite (2a, 3a, 4a, 5a) have an average diameter between 13 microns and 16 prn and a mean length of between 30 mm and 60 mm.

11) Panel (10) according to one of the preceding claims, characterized in that said at least one carrier (1) impregnated by said thermcdurcissable die (9) comprises non-woven iesdits (2, 3, 4, 5) superposed Seion a fraction mass between 15 and 25% and said matrix in a weight fraction of between 75 and 85%.

12) Panel (10) according to one of the preceding claims, characterized in that said thermosetting matrix (9) comprises:

- Seion a mass fraction of between 50 and 65%, a water-based resin selected from the group consisting of resins

melamine formaldehyde, phenolic resins and coiies wood and which is preferably a melamine-formaldehyde resin;

- in a mass fraction of between 3 and 15%, a blowing agent for the formation of open cells which preferably comprises isobutane or i'isopentane;

- in a mass fraction of between 0.5 and 2%, a catalyst preferably comprising the amine hydrochloride; and

- in a mass fraction between 30 and 45%, an aqueous solvent such as water.

13} panel (10) according to one of the preceding claims, characterized in that said non-woven (2, 3, 4, 5 bunk} and impregnated with said thermosetting matrix (9) have a density between 60 kg / m 3 and 1200 kg / m 3 and a thickness of between 5 mm and 30 mm.

14) Panel (10) according to one of the preceding claims, characterized in that the panel further comprises:

- at least an aluminum foil located outside said superposed nonwovens said at least one support (1). and or

- an outer layer forming a panel of the protective coating which is selected from the group consisting of rubbers, thermoplastic elastomers, epoxy paints and polyurethanes.

15) Panel (10) according to one of the preceding claims, characterized in that the panel has a lower thermal conductivity or brightens 50 mW m -1 K -1 and / or a sealing at cryogenic fluids and / or resistance to fire and flames.

16) coating structure (20) of a wall to impart to said wall a thermal insulation vis-à-vis of cryogenic fluids and / or protection against the fire and the flames and / or

sealing said cryogenic fluids, ia structure being particularly suitable for coating a platform, a bridge or a hull of a floating production unit liquefied gas offshore,

characterized in that the structure comprises a panel assembly (10) according to any preceding claim which is intended to be fixed to said wall panels being interconnected by sealed connecting means (13) preferably comprising composite cords basic basalt short fibers (2a, 3a, 4a, 5a) impregnated with a thermosetting matrix cell (9) identical or different from that of said panels.

17) A method of manufacturing a panel (10) according to one of claims 1 to 15, characterized in that the method comprises the following successive steps;

a) needling said non-woven (2, 3, 4, 5) overlapping said at least one support (1)) in said overlay thickness (e) without the addition of thermoplastic fibers, preferably with addition of basalt continuous fibers ( 8)

b) impregnation with said thermosetting matrix (9) of said superposed non-woven and needle,

c) calendering said non-woven impregnated,

d) drying said non-woven impregnated and calendered, and e) pressing said non-woven impregnated, dried and calendered between heated platens controlled spacing.