EP2448733A1 - Naturfaser und harzverbundstoff - Google Patents

Naturfaser und harzverbundstoff

Info

Publication number
EP2448733A1
EP2448733A1 EP10745371A EP10745371A EP2448733A1 EP 2448733 A1 EP2448733 A1 EP 2448733A1 EP 10745371 A EP10745371 A EP 10745371A EP 10745371 A EP10745371 A EP 10745371A EP 2448733 A1 EP2448733 A1 EP 2448733A1
Authority
EP
European Patent Office
Prior art keywords
fibers
natural
nonwoven
weight
lignin
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.)
Granted
Application number
EP10745371A
Other languages
English (en)
French (fr)
Other versions
EP2448733B1 (de
Inventor
Antonio Pizzi
Raphaël KUENY
Frédéric LECOANET
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.)
Universite de Lorraine
Original Assignee
Universite Henri Poincare Nancy I
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 Universite Henri Poincare Nancy I filed Critical Universite Henri Poincare Nancy I
Publication of EP2448733A1 publication Critical patent/EP2448733A1/de
Application granted granted Critical
Publication of EP2448733B1 publication Critical patent/EP2448733B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27N—MANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00—Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08—Moulding or pressing
    • B27N3/10—Moulding of mats
    • B27N3/12—Moulding of mats from fibres

Definitions

  • the present invention relates to a composite material based on natural fibers and resins, its manufacturing process and its use.
  • a composite material is an assembly of at least two immiscible materials but which have a high adhesion capacity. It consists of a matrix and a reinforcement, the latter ensuring the mechanical strength, while the matrix ensures the cohesion of the structure and the retransmission of the forces towards the reinforcement.
  • the reinforcements are in the form of fibers, for their good tensile strength and low resistance to compression.
  • the most commonly used fibers are fiberglass, carbon, aramid (Kevlar®) and silicon carbide, glass fibers being currently the most used because of their low cost.
  • the matrices mainly used for organic matrix composites are polyester resins (the most common), vinylester, epoxy, phenolic resins or thermoplastic resins such as polypropylene or polyamide which are all materials from the petrochemical industry.
  • polyester resins the most common
  • vinylester vinylester
  • epoxy epoxy
  • phenolic resins thermoplastic resins
  • polypropylene or polyamide which are all materials from the petrochemical industry.
  • metal matrix composites aluminum or magnesium is frequently used.
  • thermosetting polymers which makes them difficult to recycle, a constraint that goes against sustainable development.
  • the main natural resins used in the wood industry are adhesives based on vegetable tannin, lignin and more recently based on soy protein (Pizzi (2006) already cited).
  • the tannin-based adhesives have the advantage of not requiring reinforcement by another resin derived from petroleum (Pizzi (2006) already cited), as is the case for lignin (Lei et al., (2008) J. Appl Polym ScL, 107 (1), 203-209, Pizzi et al (1993) Holzforschung, 47, 439-445, Pizzi et al (1993) Holzaba, 47, 501-506, El Mansouri and al (2007) J.
  • Semi-natural composites materials comprising a matrix based on resin and a reinforcement of natural fibers usually derived from plants (hemp, flax, sisal, jute, etc.) or cellulose (wood fiber) and which contribute to respect of the environment have developed.
  • These semi-natural composites used in tissue engineering, in cosmetic and orthodontic applications, in furniture, sports and transportation are not fully biodegradable due to the presence of "classic" type resin from petrochemicals (polyester, epoxy ...), and are still difficult to recycle. This constraint runs counter to sustainable development.
  • the subject of the present invention is a natural composite, comprising a) a nonwoven reinforcement made of natural fibers or fibers derived from biomass, chosen from the group comprising:
  • - vegetable fibers such as flax, hemp, kenaf, sisal, jute, ramie, nettle, bamboo fibers derived from bamboo de-grinding,
  • cellulosic fibers derived from biomass for example viscose fibers
  • said fibers being used in monocomponents or in a mixture to combine the specific properties of the fibers with each other and
  • a natural matrix selected from mixtures of tannins and lignin of low molecular weight pre-reacted with an aldehyde, in a proportion of between 100/0 and 30/70 by weight of total solids, the resin representing between 20 and 50% by weight of the total weight of the composite.
  • the term "natural composite” is intended to mean a composite in which the non-natural materials, in particular those resulting from petrochemistry, such as polyisocyanates, represent at most 5% by weight relative to the total weight of the final composite, advantageously less of 4% by weight on the total weight of the final composite.
  • the proportion between tannin and lignin is 60/40, advantageously 50/50.
  • all natural tannins can be used, including tannins of mimosa, acacia, pine, pecan, quebracho, spruce and gambier.
  • Tannins are plant polyphenolic compounds that fall into two broad categories: hydrolysable tannins and condensed tannins.
  • the structural units of condensed tannins are flavanoids.
  • Condensed tannins are widely used for bonding wood derivatives to replace phenol.
  • Tannins of mimosa are obtained from the bark. These consist mainly of monoflavanoids. The most important component, which constitutes 70% of mimosa tannins, is resorcinol-pyrogallol. The second, representing 25% of mimosa tannins, is resorcinol-catechol. In smaller proportions, phloroglucinol-pyrogallol and phloroglucinol-catechol as well as "nontannins" (carbohydrates, etc.) are present.
  • Pecan tannins for their part, consist mainly of polyflavanoids phloroglucinol type.
  • the lignin has a maximum molecular weight of between 400 and 10,000, advantageously between 600 and 2,500.
  • the lignin pre-reacted with an aldehyde is glyoxalinated lignin.
  • the resin used in the natural composite may furthermore comprise usual additives known to those skilled in the art, for example
  • curing agents selected from the group consisting of hexamine, glyoxal, furfural and furfuryl alcohol and fillers.
  • the total unnatural additives must not exceed 5% by weight on the total weight of the final composite and advantageously represent less than 4% by weight relative to the total weight of the final composite.
  • Nonwovens are defined as cohesive webs (as opposed to a wadding) obtained without having to go through the intermediate spinning stage. Nonwovens are characterized by:
  • the fibers used in nonwoven are exclusively natural or derived from biomass and chosen from
  • - vegetable fibers such as flax, hemp, kenaf, sisal, jute, ramie, nettle, bamboo fibers derived from bamboo de-grinding,
  • cellulosic fibers derived from biomass for example viscose fibers, and
  • Nonwovens are prepared by conventional methods known to those skilled in the art. These methods always include two steps, a step of obtaining the veil and a consolidation step.
  • the veil or the sheet can be obtained by:
  • the veil Once the veil is manufactured, it must be consolidated because it still has no cohesion. This second step is called consolidation. Precisely, it is the process of binding the fibers in the veil to increase the strength. As for the first step, there are different ways to consolidate the veil to obtain a sheet (or mat):
  • the nonwoven has been consolidated by mechanical needling or reinforcement by sewing thread of natural or knitted fibers (Malimo type process).
  • the composites may further comprise a woven reinforcement based on natural fibers, to optimize its reinforcing function or for a matter of appearance.
  • multilayer composites may be envisaged comprising a reinforcement comprising either a layer of nonwoven needled / a layer of woven natural fibers / a layer of nonwoven needled or a layer of woven natural fibers / a layer of nonwoven Needled woven / a layer of woven natural fibers.
  • woven in natural fibers we can use twill, satin, canvas, ripstop or 3D fabric weave (spacer).
  • the composites according to the invention can be manufactured by any technique known to those skilled in the art to obtain monolayer or multilayer structures.
  • the subject of the invention is also a method for preparing a composite, characterized in that it comprises:
  • a) a step of preparing the nonwoven comprising preparing a veil from natural fibers or from biomass selected from the group comprising:
  • - vegetable fibers such as flax, hemp, kenaf, sisal, jute, ramie, nettle, bamboo fibers derived from bamboo de-grinding,
  • cellulosic fibers derived from biomass for example viscose fibers, and
  • said step being followed by the consolidation of said web to obtain a nonwoven in the form of a web, optionally reinforced with a fabric of natural fibers in the nonwoven or on the surface,
  • the natural matrix selected from the group comprising mixtures of tannin with lignin of low molecular weight, pre-reacted with an aldehyde, in a proportion of between 100/0 and 30 70% by weight of the total solids, the resin representing between 20 and 50% by weight of the total weight of the composite.
  • the consolidation is carried out mechanically, in particular by needling or binding by sewing thread or knitting (Malimo type process).
  • the composites according to the invention can be used for the production of industrial materials, in particular panels.
  • the subject of the invention is also a process for preparing panels based on a natural composite, characterized in that it comprises:
  • a) a step of preparing the nonwoven comprising preparing a veil from natural fibers or from biomass selected from the group comprising:
  • cellulosic fibers derived from biomass for example viscose fibers, and
  • the resin representing between 20 and 50% by weight of the total weight of the composite and
  • any technique known to those skilled in the art and applicable to composites, in particular pressing by pressing or pressing processes specific to composite materials, such as, for example, the infusion method or the RTM process may be used.
  • the method of infusion uses in particular, a mold, a vacuum cover and a vacuum device necessary to diffuse the resin in the textile complex and provide the pressure necessary to take the resin; the device will be installed in an oven or under heat lamps to obtain the necessary crosslinking temperature.
  • the RTM process by injecting resin into a closed heating mold is also a suitable solution.
  • the panels obtainable by the process of the invention are also part of the invention. They can either be of low density and thick (8 mm and more), or be thin and of high density.
  • the present invention also relates to the use of the natural composite according to the invention for the production of industrial materials or objects likely to be used in industry, in particular in the furniture industry, the automotive industry, the industry nautical industry, the aviation industry, the sports and leisure industry, the building industry and the manufacture of equipment parts.
  • FIG. 1 represents the gel time of the tannin matrix of mimosa / hexamine at 100 ° C. as a function of the pH of the matrix.
  • Figure 2 shows the average of the results obtained in mechanical tests, cold water swelling and Brinell hardness for high density thin composites and low density thick composites made of non-woven fabric made of non-woven fabric.
  • Figure 3 shows the effect of corona treatment on the average of the results obtained in the mechanical tests.
  • FIG. 4 represents electron microscopic images at a magnification of 8000 for (a) untreated linen fibers, (b) flax fibers after 15 minutes of corona treatment and (c) flax fibers after 30 minutes of corona treatment.
  • Figure 5 shows electron microscopic images of a low density composite showing how the resin covers the flax fibers of the composite.
  • FIG. 6 illustrates the contact angle and its variations as a function of time for (a) a non-woven linen mat, (b) a nonwoven mat of linen subjected for 15 minutes to a corona treatment (c). ) a low density thin composite and (d) a high density thin composite.
  • the time is expressed in minutes.
  • FIG. 7 illustrates the variations of modulus of elasticity as a function of time and temperature as measured by thermomechanical analysis of the treatment of the tannin-hexamethylenetetramine matrix.
  • FIG. 8 shows a thermoformed composite obtained from 6 layers of nonwoven mats made of linen impregnated with a tannin-hexamine / lignin glyoxalized matrix according to the invention.
  • a non-woven linen is prepared on a fiber preparation line and mixed with the other fibers in the case of production. of a multicomponent.
  • the veil is formed on a conventional nonwoven card with conventional output, condenser or random depending on the desired orientation of the fibers, then a lapper spreader is used to increase the thickness of the finished product and the binding is done by needling
  • the nonwovens are stored in a room with a humidity set to
  • the pH of the fibers measured by immersing them in distilled water is 6.04.
  • the lignin used is extracted from the wheat straw. It is about lignin organosolv, lignin of low molecular mass (approximately 1200-1250 g / mol) provided by the Industrial Company of the Vegetal Matter of Reims.
  • Kenyan mimosa tannin extracts used have a Stiasny index of 92.2 and are supplied by Silva Chemica.
  • a 45% solution of tannin is prepared in water and the pH is adjusted to 10.4 with a 33% aqueous sodium hydroxide solution.
  • To this tannin solution is added a 30% aqueous solution of hexamethylenetetramine (hexamine) as a curing agent so that hexamethylenetetramine (hexamine) is 5% by weight of tannin.
  • hexamine hexamethylenetetramine
  • Impregnation of the nonwovens is performed manually on mats of 30 cm x 35 cm, in a container filled with a matrix solution prepared according to Example 1.1.4 or 1.1.5.
  • This test is performed on the faces of the composite using specimens of size 300 x 25 mm according to the French standard NF B 51-123 used for glued wood panels to determine the modulus of elasticity (MOE) in tension and the resistance traction parallel to the faces.
  • the tests are performed on an INSTRON® universal testing machine.
  • An extensometer of 0.001 mm sensitivity is coupled to the test to measure the elongation of the sample during the test and to calculate the MOE.
  • the specimen is centered between the jaws of the test device and a load is applied continuously at a constant speed.
  • the test is completed and the computer records the maximum force reached (Fmax) in N.
  • the modulus of elasticity in tension is expressed in MPa and the tensile strength is calculated by the following formula:
  • HB (3.18 / 1000) x (F / P) where F, expressed in newtons, represents the force determining the restraint retained and P, expressed in millimeters, is the depth of penetration of the ball.
  • the contact angle and its variation as a function of the time of fall on the tannin-hexamine matrix of the non-woven mat is measured with an FM40 Easy Drop apparatus from Krûss.
  • the protocol remains the same as for the resins, except that the "sandwich” is replaced by a 20x5 mm test panel. From the curve obtained, it can be inferred a Tg glass transition temperature (0 C) because this phenomenon is accompanied in particular an increase in the free volume, and thus the expansion coefficient.
  • the measurement of the contact angle accounts for the ability of a liquid to spread over a surface by wettability.
  • the method consists in measuring the angle of the tangent of the profile of a drop deposited on the substrate, with the surface of the substrate. This measurement makes it possible to measure the surface energy of the liquid or the solid.
  • the measurement of the contact angle makes it possible to know if a material is hydrophilic (has an affinity with water) or hydrophobic. The higher the angle ⁇ , the less the drop will spread, the less the material will be wettable so it is impermeable (hydrophobic). The drop of water is deposited very gently using a syringe of greater or lesser diameter depending on the nature of the test material.
  • the value that is significant is the first, that is, when the drop comes in contact with the material.
  • the evolution of the drop as a function of time can deduce a time of absorption of the drop by the material
  • the anhydrous test pieces are measured and then immersed in water. Dimensional changes are measured after 2 hours and 24 hours.
  • the swelling (G) is calculated according to the following formula:
  • ti is the thickness of the specimen before immersion, in millimeters
  • t 2 is the thickness of the specimen after immersion, in millimeters
  • CORONA is used here to increase the surface condition of fibers (NM Belgacem, P.Bataille, Sapieha S., Journal of Applied Polymer Science, 1994, 53, 379-385) and modify the surface condition of fibers to improve the fiber / matrix interface (D.Sun, GK Stylios, J. Mat., Processing Technologies, 2006, 173-182).
  • the gel time of the tannin / hexamine matrix follows the curve given in FIG. 1. That of the matrix obtained in example 1 is 10 min 54 s for a pH of 9.40.
  • the average dry extract is 57% and the maximum modulus of elasticity is 4400 MPa.
  • the gel time at 100 ° C. is greater than 4 hours and the dry extract of the matrix is 32.1%. 1.2.2. Properties of the non-woven
  • the nonwoven linen obtained in Example 1 has an average basis weight per mat of 643 g / m 2 at 13% moisture and the nonwoven hemp obtained in Example 1 has an average basis weight per mat of 386 g / m 2 at 16% humidity.
  • the impregnated mats obtained in Example 1 are superposed by two to prepare the high density thin laminates and by eight to prepare the low density thick laminates.
  • the assemblies thus formed are pressed at a pressure temperature of 200 ° C., with a maximum pressure of between 2.6 and 4.4 MPa '(27 and 45 kg / cm 2 ) followed by a reduction in the pressure of first at about 1.5-1.8 MPa (15-18 kg / cm 2 ) and then at 0.5-1 MPa (5-10 kg / cm 2 ) for a pressing time of 5 minutes.
  • the press is allowed to press the mat to the maximum to produce a thickness of 1.2 mm.
  • Composites of lower density are prepared under the same pressing conditions but are pressed in the presence of stoppers, 8 mm thick steel bars, so as to control the density and the thickness of the composite.
  • the solid resin content after pressing is between 30 and 50% of the total weight of the mat for the low density mats and between 20 and 40% of the total weight of the mat for the high density mats.
  • the modulus of elasticity (MOE) in tension and tensile strength as well as the tensile strength obtained for panels made from composites based on linseed and mimosa / hexamine tannin are given in the table of the figure. 2.
  • the results obtained for both thick (8 mm) low density composites and thin (1.2 mm) high density composites are good.
  • the modulus of elasticity of the composites tends, in both types of test (in tension and in tension) to be directly correlated to the density of said composite, the correlation between the density and the MOE values being approximately linear.
  • the average tensile strength at break for the low density composites is also related to the density of the composite, but in a different way compared to the modulus of elasticity.
  • the average breaking stress is 16 MPa.
  • the swelling seems to depend on the relative proportion of fibers in the composite.
  • the swelling observed at 24 hours is the same in all cases, the thick or thin composites having a swelling of the order of 20-22%.
  • the swelling at 2 hours shows more variation, the high amount of fibers per unit volume in the high density composites resulting in a higher initial swelling rate.
  • Brinell hardness is also dependent on the density of the composites.
  • the hardness of the composites according to the invention is about 5 to 10 daN / mm 2 for the thin high density composite and about 2 to 5 daN / mm 2 for the low density thick composite; these values are good compared to that of coniferous wood, which is generally around 1.6 daN / mm 2 , to that of hardwood, which is between 2.6 and 7 daN / mm 2, and to that of panels. wooden slats melamine which is about 1.9-2.0 daN / mm 2. 2.2.4. thermoforming
  • thermoplastic behavior of the resin matrix formed by a 50/50 mixture by weight of a glyoxalinated low molecular weight lignin and a tannin + hexamine is given in FIG.
  • Fig. 4a shows the fiber before treatment.
  • Corona treatment renders the surface of the fibers rougher by increasing their surface layers (Fig. 4a-c).
  • Such a surface should improve both the mechanical adhesion of the resin and increase the surface of the substrate leading to improved secondary adhesion forces of the resin on the substrate.
  • the modulus of elasticity (MOE) of the flexural and tensile composites and the maximum tensile strength at failure do not appear after the same length in case of corona treatment.
  • the two MOEs have a maximum value after about 10 minutes of treatment, the small improvement of MOE in flexion from 10 to 15 minutes of treatment and not significant (see Figure 3).
  • the tensile strength at break of the composite reaches its maximum sooner, after about 5 minutes of corona treatment and then decreases rapidly.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Reinforced Plastic Materials (AREA)
EP10745371.4A 2009-07-01 2010-06-29 Naturfaser und harzverbundstoff Not-in-force EP2448733B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0903233A FR2947572B1 (fr) 2009-07-01 2009-07-01 Materiau composite a base de fibres et de resine naturelles
PCT/FR2010/051360 WO2011001105A1 (fr) 2009-07-01 2010-06-29 Materiau composite a base de fibres et de resine naturelles

Publications (2)

Publication Number Publication Date
EP2448733A1 true EP2448733A1 (de) 2012-05-09
EP2448733B1 EP2448733B1 (de) 2013-06-05

Family

ID=41728205

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10745371.4A Not-in-force EP2448733B1 (de) 2009-07-01 2010-06-29 Naturfaser und harzverbundstoff

Country Status (3)

Country Link
EP (1) EP2448733B1 (de)
FR (1) FR2947572B1 (de)
WO (1) WO2011001105A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018047047A1 (en) * 2016-09-07 2018-03-15 Domtar Paper Company, Llc Glyoxalated lignin compositions

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FR2966171B1 (fr) * 2010-10-18 2013-12-27 Univ Nancy 1 Henri Poincare Materiau souple a base de fibres et de resines naturelles
FI124944B (fi) 2011-04-08 2015-03-31 Upm Kymmene Corp Menetelmä sideainekoostumuksen valmistamiseksi, sideainekoostumus, liima-ainekoostumus, kerrostettu komposiittirakenne, ja sideainekoostumuksen ja liimakoostumuksen käyttöjä
CN102391659B (zh) * 2011-09-13 2013-11-13 南京林业大学 一种发泡苯乙烯板的界面浸渍液
US20130183484A1 (en) * 2012-01-12 2013-07-18 E I Du Pont De Nemours And Company Core structures comprising tannin resin
MY195798A (en) 2013-12-20 2023-02-21 New Zealand Forest Res Institute Limited Adhesive
FI130116B (en) * 2018-09-21 2023-03-03 Woodio Oy Process for the production of shaped products
CN109968699B (zh) * 2019-04-11 2024-05-28 大庆市九天新型保温建筑材料有限公司 斜面缝扎机及其制作的缝扎网织增强纤维保温板

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GB582707A (en) * 1942-03-16 1946-11-26 African Sisal & Produce Compan Process for the manufacture of paper pulp and other products from the fleshy parts of sisal and similar plants
DE19603330C1 (de) * 1996-01-31 1997-06-05 Bayer Ag Verfahren zur Herstellung von Holzwerkstoffen mit Polyisocyanat-Bindemitteln unter Mitverwendung von latenten, wärmeaktivierbaren Katalysatoren
DE69823338T2 (de) * 1997-02-20 2004-08-26 Kronospan Technical Co. Ltd. Klebstoffzusammensetzung und ihre verwendung
JP2007044908A (ja) * 2005-08-08 2007-02-22 Toyota Auto Body Co Ltd ボード材の製造方法
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018047047A1 (en) * 2016-09-07 2018-03-15 Domtar Paper Company, Llc Glyoxalated lignin compositions

Also Published As

Publication number Publication date
EP2448733B1 (de) 2013-06-05
FR2947572B1 (fr) 2011-08-26
WO2011001105A1 (fr) 2011-01-06
FR2947572A1 (fr) 2011-01-07

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