WO2015143497A1 - Fibres de carbone obtenues à partir de matières premières biopolymères - Google Patents

Fibres de carbone obtenues à partir de matières premières biopolymères Download PDF

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Publication number
WO2015143497A1
WO2015143497A1 PCT/AU2015/050074 AU2015050074W WO2015143497A1 WO 2015143497 A1 WO2015143497 A1 WO 2015143497A1 AU 2015050074 W AU2015050074 W AU 2015050074W WO 2015143497 A1 WO2015143497 A1 WO 2015143497A1
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Prior art keywords
accordance
fibre
precursor
mean diameter
nanocellulose
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PCT/AU2015/050074
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English (en)
Inventor
Darren Martin
Eric Mcfarland
Pratheep Kumar ANNAMALAI
Bronwyn Laycock
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The University Of Queensland
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Priority claimed from AU2014901123A external-priority patent/AU2014901123A0/en
Application filed by The University Of Queensland filed Critical The University Of Queensland
Publication of WO2015143497A1 publication Critical patent/WO2015143497A1/fr

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D01F9/17—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate from lignin

Definitions

  • the present invention relates to production of carbon fibres.
  • Carbon fibres are strong, with an extremely high ratio of strength-to-volume, and are lighter than steel. This makes their use in composites ideally suited to applications where strength, stiffness, lower weight, and outstanding fatigue characteristics are critical requirements. They also can be used when high temperature, chemical inertness and high vibration damping are important. For these reasons, carbon fibre reinforced composites are now used in a wide range of industries, such as lightweight, fuel efficient automobile and aircraft components. The demand for carbon fibre in the automotive sector alone has been projected to more than triple from 3,400 tonnes in 2012 to 12, 100 tonnes in 2017.
  • Carbon fibres are generally made from high grade polyacrylonitrile (PAN), an expensive, petroleum derived polymer that accounts for -50% of the cost of manufacturing. Approximately 20 % of the production cost is attributed to the energy input that is made significant due to the use of heating processes in carbonisation and graphitisation steps. Consequently, the production cost of carbon fibre could be decreased significantly with the adoption of a lower cost raw material precursor for the carbon and a decrease in the energy input required, such as would be achievable with lower processing temperatures.
  • PAN polyacrylonitrile
  • other less expensive petroleum derived fibres such as polyethylene and polypropylene and other low cost polymers has led to sub-optimal mechanical properties.
  • thermoplastics including polyethylene (PE) and polypropylene (PP)
  • the precursor polymer fibres are spun from a melt prior to being pyrolysed.
  • PE polyethylene
  • PP polypropylene
  • the use of plant derived raw materials offers the opportunity for not only bringing down the cost, but also for decoupling from the cost volatility of petroleum in addition to the environmental and supply chain security benefits provided by a renewable and sustainable feedstock.
  • cellulose-derived carbon fibres are known, their share of the market has also been limited by their comparatively poor performance, particularly tensile strength, due to imperfect fibre structure.
  • extensive pre-processing is typically required, adding significantly to costs.
  • the poor mechanical properties of carbon fibres derived from cellulose may, in part, be derived from the fact that efforts to produce carbon fibres from cellulose to date have employed cellulose materials composed of agglomerates of smaller diameter primary nanofibrils.
  • the interfaces between primary nanofibrils in an agglomerated fibre can act as conduits for crack propagation, reducing the resistance of the material to mechanical failure under stress.
  • Agglomerates are particularly prolific in cellulose materials derived from higher plants which are also perhaps the most attractive types of cellulose for industrial applications due to their lower cost compared to cellulose from other sources such as bacteria, algae and tunicates.
  • higher plants is well known and includes vascular plants including those that have roots and produce flowers or seeds such as grasses and other members of the superphylum Tracheata. Algae is classified as a "lower plant”.
  • Cellulose materials derived from higher plants and with fibre diameters as small as 50 nm have been used as precursors for carbon fibres however even these fibres are agglomerates of smaller diameter primary fibres that have diameters below 5 nm.
  • biopolymers such as plant material for the production of carbon fibres has the potential to both reduce cost and improve the sustainability of the production cycle.
  • Cellulose has a number of significant advantages, such as having a very well-ordered crystal structure and being able to thermally decompose without melting.
  • Natural fibres such as cotton and ramie, are less desirable for carbonization because of their discontinuous filament structure, and low degree of orientation and impurities arising from the complex structure of natural cellulose sources such as lignin and hemicellulose.
  • New processing techniques are able to make continuous fibres from natural cellulose fibres which have ordered crystalline structures. Cellulose undergoes thermal decomposition without melting.
  • cellulosic precursors have high thermal conductivity, high purity, mechanical flexibility and low precursor cost although mechanical properties are still inferior to PAN-derived fibres.
  • cellulose derived fibres have low carbon yields and do not have sufficient tensile strength for widespread use. Extensive pre-processing is also typically undertaken, which adds significantly to costs. While cellulosic materials are used as carbon precursors on a large scale, their use is mostly limited to activated carbon as an adsorbant and not as a source for producing carbon fibres.
  • Carbon fibres formed by the processing of agglomerated fibrils of cellulose typically result in carbon fibre with poor mechanical properties since the low strength associated with the interface between fibrils in the cellulose agglomerate is typically transferred to the resulting carbon fibre structure. That is, the resulting carbon fibre typically consists of agglomerated carbon fibrils where the bond strength between adjacent fibrils is poor, leading to poor overall mechanical properties in the carbon fibre. Furthermore, carbon fibres produced in a typical carbonisation process typically have significantly reduced volume relative to the cellulose precursor used such that the diameter of the carbon fibre is less than that of the original cellulose fibre.
  • the present invention is directed to production of carbon fibres, which may at least partially overcome at least one of the abovementioned disadvantages or provide the consumer with a useful or commercial choice.
  • the present invention in one form, resides broadly in a method of producing carbon fibre, the method comprising the steps of:
  • the carbonising results in formation of fibrillar nanostructures such that the mean diameter of the fibrillar nanostructures is less than or equal to the mean diameter of the nanocellulose fibrils.
  • the carbonising results in formation of a first group and a second group of fibrillar nanostructures, wherein the mean diameter of the first group of fibrillar nanostructures is greater than the mean diameter of the nanocellulose fibrils and the mean diameter of the second group of fibrillar nanostructures is less than or equal to the mean diameter of the nanocellulose fibrils.
  • the nanocellulose fibrils have a mean diameter of less than 40 nm and preferably less than 30 nm, more preferably less than 20 nm.
  • the nanocellulose fibrils have a mean diameter of less than 10 nm, preferably less than 8 nm and more preferably less than 5 nm.
  • the nanocellulose fibrils are derived from higher plants.
  • references to a specific fibril or fibre diameter do not mean that all of the fibres or fibrils within a sample of material have a diameter of specifically that value. Rather, samples of material typically contain a distribution of fibril/fibre diameters and the diameter value quoted refers to a mean value of the diameter.
  • the diameter of fibrils and fibres is typically measured using imaging methods such as scanning electron microscopy (SEM) or transmission electron microscopy (TEM) in which a number of fibres/fibrils within a population are measured in order that a reasonable estimate of the mean diameter can be developed. Therefore, the mean diameter may be calculated on a number-average basis.
  • SEM scanning electron microscopy
  • TEM transmission electron microscopy
  • the solution or dispersion of the first or second aspect may comprise an aqueous medium.
  • a carbon fibre which is formed from spinning precursor fibre filaments from an aqueous dispersion of nanocellulose fibrils (without the addition of any other additional polymer) and carbonising those precursor fibres is highly advantageous in that it alleviates the need for using organic solvents such as dimethyl formamide (DMF).
  • organic solvents are typically used in prior art processes for forming carbon fibres known in the art.
  • the present invention presents a significant economic advantage over prior art methods in providing a method for producing carbon fibres that reduces and preferably alleviates the need to use organic solvents.
  • the precursor fibre filaments are composite fibre filaments comprising nanocellulose fibrils and further comprising another polymer.
  • the nanocellulose fibrils may be dispersed in a polymer melt.
  • the polymer may comprise one or more polymers including, but not limited to the following: Polyacrylonitrile (PAN), Polyethylene (PE), Lignin, Polypropylene, Polyacrylonitrile-methyl acrylate copolymers (PAN-MA), poly [acrylonitrile-co-itaconic acid] copolymers, poly[acrylonitrile-co-acrylamide] copolymers, Pitch, and other established carbon fibre precursors.
  • the polymers may also include polyolefins, including polyethylene, polypropylene, polymethylpentene, polybutene, polyisobutylene and Polyesters such as Polyhydroxyalkanoates (PHAs), Polylactic acid (PLA) and Polycaprolactone (PCL).
  • PHAs Polyhydroxyalkanoates
  • PLA Polylactic acid
  • PCL Polycaprolactone
  • the use of low cost nanocellulose fibrils in combination with other more expensive polymer fibres such as PAN can lower the cost of carbon fibre production and decrease reliance on petrochemical derived raw materials.
  • the use of nanocellulose fibrils with favourable mechanical properties in combination with other polymers that would otherwise have insufficient mechanical properties to be used in certain applications may result in carbon fibres with improved mechanical properties over carbon fibres derived from the polymers had the nanocellulose fibrils not been present. This results from the superior mechanical properties provided by the carbon derived from nanocellulose fibrils.
  • the lower limit of fibre diameter that can be drawn from a polymer melt is limited by the mechanical properties of the melt since small diameter polymer melts are more fragile and prone to breakage than larger polymer melt fibres.
  • a polymer melt with poor mechanical properties may be unable to produce small fibre diameters during melt spinning demanded by many applications.
  • the addition of nanocellulose fibrils to a polymer melt may provide additional strength to the melt, reinforcing it and enabling finer fibres to be spun. This approach then may enable the adoption of polymer alternatives to PAN that would otherwise not be viable without the use of the nanocellulose fibrils.
  • the precursor fibre filaments comprising the polymer melt described above may be spun by wet spinning nanocellulose fibrils/polymer blends in organic solvents.
  • the organic solvents may be selected from solvents including, but not limited to Dimethylformamide (DMF) or Dimethyl Sulfoxide (DMSO). Such spinning is known as organic wet spinning.
  • the precursor fibre filaments may be spun by melt spinning polymers such as lignin and/or polyethylene blended with nanocellulose fibrils.
  • melt spinning polymers such as lignin and/or polyethylene blended with nanocellulose fibrils.
  • lignin to the nanocellulose fibrils improves melt spinnability and processability of the produced carbon fibres because lignin is melt processable in its own right, with melt flow assisting fibrillary alignment, and, having a high aromatics content, promoting cross-linking.
  • the precursor fibre filaments may be spun by spinning of continuous fibres from an aqueous dispersion of the nanocellulose fibrils.
  • the precursor fibre filaments may be impregnated with a carbonization enhancing additive such as an organo-silicone additive.
  • spinning enhancing agents such as polyethylene oxide, polyvinyl alcohol or an amine group containing compound may be added to the solution or the dispersion. Furthermore, such agents may also be added to disrupt hydrogen bonding in the solution or the dispersion thereby resulting in improved elongation and processing of the precursor fibre filaments.
  • the invention provides a method of producing carbon fibre, the method comprising the steps of
  • the nanocellulose fibrils may be pre-treated by a pre- treatment process such as a halogenation pre-treatment step.
  • the halogenation pre-treatment may comprise contacting the nanocellulose fibrils with a halogen and/or a halogen derivative to form a nanocellulose fibril-halogen mixture and heating the mixture to a heating temperature of at least 80°C for a heating time period of at least 10 minutes; thereby forming halogenated nanocellulose fibrils.
  • the halogenation pre-treatment step may be utilised for bromination and/or iodisation and/or chlorination.
  • the halogenation step may further comprise the step of irradiating the nanocellulose- halogen mixture under visible and/or ultraviolet and/or infra-red radiation for promoting halogenation of the nanocellulose fibrils.
  • halogenation pre-treatment step may be used for pre-treating the precursor fibre filaments spun from nanocellulose fibrils as discussed in the first and second aspects.
  • the halogenation pre-treatment step may also be used for pre-treating the nanocellulose fibrils directly in conjunction with the third aspect of the present invention.
  • the carbonizing step is preceded by a stabilisation step wherein the precursor filaments are heat treated at an intermediate stabilisation temperature.
  • the precursor fibres may be stabilised by heating and stretching in a heating chamber with well controlled gas flow. This stabilisation process is commonly introduced to induce
  • the process further comprises a graphitization step.
  • the graphitisation step is carried out at a graphitisation temperature that is equal to or greater than the elevated carbonisation temperature
  • the precursor fibre filaments may be oriented in a preferred orientation by mechanical means such as stretching to apply tension. The step of applying tension to the precursor fibre filaments helps in maintaining the fibre filaments in a desirable orientation and/or reduces variation in longitudinal dimension of the fibre filaments.
  • the method further comprises a processing step for enhancing carbon bonding strength in the precursor fibre filaments.
  • Carbon bonding strength may be enhanced by adding metal ions (in solution form such as V + ; Cr ++ ; Mn + ; Fe ++ ; Co + ; Ni ++ ; Cu + ).
  • Addition of metal ions may also be balanced by addition of halogenated compounds such as bromides and chlorides.
  • the metal ions may be added in the form of adding a metal solution containing one or more compounds or mixtures of compounds including but not limited to chlorides, bromides, iodides, nitrates, sulphates, phosphates with metals including but not limited to Fe, i, Co, Cu, Sn, Sb, Mn, Cr, V, Ti .
  • the metal ions are preferably added to the precursor fibre prior to the carbonisation step.
  • the metal ions may be impregnated into the precursor fibre filaments, for example by contacting the precursor fibre filaments with a solution containing the metal ions.
  • one or more catalysts may be added or applied for catalysing stabilisation and/or carbonisation of the precursor filaments.
  • the catalysts may contain metals or mixtures of metals including but not limited to zinc, gallium, In, Sn, Sb, Bi, Cu, Ni, Co, Fe, Ru, Mn, Cr, V, Ti, Al, Au, Ir, Pt, Zr, Mo, Ag, Ga, Ca, Mg, Be, Sr and non-metals, Na, K, B, S, P ,N, Se and may be in the form of oxides, halides, or reduced or partially reduced metals or mixtures of metals .
  • the step of carbonisation comprises slow pyrolysis in which temperature is increased to an initial temperature in the range of 600°C to 1500°C, more preferably 800°C to 1 100°C under an inert atmosphere (such as N 2 /Ar atmosphere).
  • the process further comprises a graphitisation wherein the carbonised fibre filaments are graphitised at a graphitisation temperature in the range of 900°C to 3000°C.
  • the carbonisation stage is preceded by a stabilisation stage of heating the precursor filaments at a stabilisation temperature in the range of 150°C to 350°C.
  • the nanocellulose fibrils have an aspect ratio of at least 250. Aspect ratio is the ratio of length to diameter of the fibrils.
  • the nanocellulose fibrils are derived from higher plants.
  • the nanocellulose fibrils are derived from plant material in which the amount of hemicellulose in the plant material is greater than the amount of lignin in the plant material. [0043] In one embodiment, the nanocellulose fibrils are derived from a grass species having C4 anatomy.
  • the nanocellulose fibrils are derived from a drought-tolerant grass species.
  • the nanocellulose fibrils are derived from arid grass species.
  • the nanocellulose fibrils are derived from Australian native arid grass known as "spinifex" .
  • Spinifex also known as 'porcupine' and 'hummock' grass
  • Triodia Triodia
  • Monodia Monodia
  • Symplectrodia not to be confused with the grass genus Spinifex that is restricted to coastal dune systems in Australia
  • Hummock grassland communities in arid Australia are dominated by spinifex species of the genus ' Triodia' .
  • Triodia Spinifex
  • Triodia also known as 'porcupine' and 'hummock' grass
  • T. Pungens has a typical composition of: cellulose 37 %, hemicellulose : 36 %, lignin: 25% and ash 4 %
  • the present invention is also directed toward the structure of the carbon fibres that result from the methods of processing described herein.
  • a cellulose precursor composed of separated nanofibrils with mean diameter less than 50 nm rather than larger agglomerates of fibrils as discussed earlier in the background section
  • the carbon fibre formation process described herein has been found to result in carbon fibres in which the individual cellulose nanofibrils may be fused or adhered together to form a carbon fibre of greater diameter than the precursor cellulose nanofibrils, rather than a more loosely bonded agglomerate.
  • the present invention is directed to carbon fibres formed by processing cellulose fibres of smaller mean diameter in comparison than the mean diameter of the resulting carbon fibre.
  • Carbon fibres formed by the processing of agglomerated fibrils of cellulose typically result in carbon fibre with poor mechanical properties since the low strength associated with the interface between fibrils in the cellulose agglomerate is typically transferred to the resulting carbon fibre structure. That is, the resulting carbon fibre typically consists of agglomerated carbon fibrils where the bond strength between adjacent fibrils is poor, leading to poor overall mechanical properties in the carbon fibre. Furthermore, carbon fibres produced in a typical carbonisation process typically have significantly reduced volume relative to the cellulose precursor used such that the diameter of the carbon fibre is less than that of the original cellulose fibre. The carbon fibres produced from the method of the present invention addresses one or more of the issues such as agglomeration and poor mechanical properties.
  • the present invention resides in carbon fibres formed from a cellulose precursor where the cellulose precursor comprises nanofibrils with diameter less than 50 nm and wherein the carbon fibres have elongate nanostructures with a mean diameter in the range of 5 nm to 200 nm and a mean length in the range of 5 ⁇ to 500 ⁇ .
  • the present invention provides a carbon fibre comprising carbonised nanocellulose fibrils, wherein prior to carbonisation, the nanocellulose fibrils have a mean diameter of less than 50 nm.
  • the present invention provides a carbon fibre comprising carbonised nanocellulose fibrils, said carbonised fibrils having a nanostructure with a mean diameter that is greater than mean diameter of the nanocellulose fibrils prior to carbonisation.
  • the diameter of the resulting carbon fibres may be smaller than that of the precursor nanocellulose fibrils.
  • the present invention resides in carbon fibres formed from a cellulose precursor where the cellulose precursor comprises nanofibrils with mean diameter less than 50 nm and wherein the carbon fibres have a mean diameter smaller than that of the cellulose precursor.
  • the invention provides carbon fibres formed from a cellulose precursor where the cellulose precursor comprises nanofibrils with mean diameter of less than 50 nm and wherein the carbon fibres have elongate nanostructures with a mean diameter in the range of 5 nm to 200 nm and a mean length in the range of 5 ⁇ to 20 ⁇ .
  • the invention provides carbon fibres formed from a cellulose precursor where the cellulose precursor comprises nanofibrils with mean diameter less than 50 nm and wherein the carbon fibres have elongate nanostructures with a mean diameter of less than 50 nm.
  • the invention provides carbon fibres formed from a cellulose precursor where the cellulose precursor comprises nanofibrils with mean diameter less than 50 nm and wherein the carbon fibres comprises a first group and a second group of carbon fibres, wherein the first group of carbon fibres have elongate nanostructures with a mean diameter of less than or equal to 50 nm and the second group of carbon fibres have elongate nanostructures with a mean diameter of more than 50 nm.
  • the invention provides a carbon fibre comprising halogenated nanocellulose fibrils that have been carbonised to form the carbon fibre.
  • the invention provides a method of producing carbon fibre, the method comprising the steps of
  • the invention also provides a method of producing carbon fibre, the method comprising the steps of:
  • the lignin may also be pre-treated before the carbonisation step by the halogenation pre-treatment step described in the previous sections.
  • Figure 1 is a flow diagram showing a process of producing carbon fibres in accordance with a first embodiment of the present invention.
  • Figure 2 is a flow diagram showing a process of producing carbon fibres in accordance with a second embodiment of the present invention.
  • Figure 3 is a flow diagram showing a process of producing carbon fibres in accordance with a third embodiment of the present invention.
  • Figures 4A, 4B and 4C show Transmission Electron Microscopy (TEM) images of nanocellulose fibrils and pyrolised nanocellulose fibrils obtained in Example 1.
  • TEM Transmission Electron Microscopy
  • Figure 5 represents the Raman spectra of freeze dried spinifex nanofibrillated cellulose (NFC) obtained after carbonisation (240 °C under air for 1 h, 800 °C under argon for 2.5 h) in Example 1.
  • Figures 6A and 6B show Scanning Electron Microscopy (SEM) images of pyrolised nanocellulose fibrils obtained in Example 1.
  • FIG. 7 shows thermogravimetric analysis (TGA) data for the cellulose nanofibrils derived from Spinifex grass as per Example 1.
  • Figure 8 shows FTIR spectra comparing samples from example 1 at different pyrolysis temperatures and time durations.
  • Figure 9 shows pictures of NFC sheets at different stages during carbonisation in accordance with Example 2.
  • Figure 10 represents the Raman spectra for carbonised spinifex NFC sheet in accordance with Example 2.
  • Figure 11 shows images of samples (including comparative examples) before and after carbonisation in accordance with Example 2.
  • Figure 12 represents thermograms of the different samples (including comparative examples) under nitrogen in accordance with Example 2.
  • Figure 13 represents TGA data of samples in accordance with Example 2.
  • Figure 14 represents TGA thermograms of the halogen absorbed samples (including comparative samples) in accordance with Example 2.
  • Figure 15 shows images of halogen absorbed samples (including comparative examples) before and after carbonisation.
  • Figure 16 TGA shows TGA thermograms of lignin and brominated lignin (with 98 wt. % increase) under nitrogen in accordance with Example 3.
  • a process (100) for producing carbon fibres in accordance with the present invention comprises an initial step (1 10) of uniformly mixing nanofibrillated cellulose (NFC) with diameter of less than 50 nm with PAN in an organic solvent, Dimethylformamide (DMF).
  • the quantity of nanocellulose added may be variable and may range from 2.5 wt% to 25 wt%.
  • the mixture may be subsequently polymerized in a polymerization step (110) to form a composite blend of PAN-nanocellulose.
  • spinning enhancing agents such as polyethylene oxide, polyvinyl alcohol or amine groups may be added to disrupt the hydrogen bonding in the composite blend.
  • the precursor fibre filaments may be obtained by organic solvent based spinning in a spinning step 120.
  • the precursor fibres as obtained may be stabilised by heating and stretching in a chamber with well controlled gas flow in a stablisation step (1001) in which the precursor fibres may undergo oxidation, dehydration and/or dehydrogenation at an elevated temperature that may lie in the range of 200°C to 350°Cfor 0.5 to 4 hours by ramping up the temperature of the chamber from room temperature at a ramping rate of 1-5 °C/min. This process creates cross- linked "ladder polymer" chains and the T g of the precursor fibre increases.
  • carbonisation (1002) of the oxidised fibres can be carried out at temperature of approximately 800°C under inert conditions (Ar/N 2 atmosphere).
  • the carbonisation step is followed by graphitisation (1003) of the carbonised fibres at temperatures ranging from 1 100°C to 3000°C while stretching the carbonised fibres to ensure preferred crystalline orientation to form carbon fibres (1004).
  • the precursor fibres Prior to or during carrying out the stabilisation step (1001), the precursor fibres may be treated with metal ion containing solutions (such as FeCl 3 , N1NO 3 , C0SO 4 etc) in a pre- treatment step. Addition of such metal ions is associated with increased stabilization rates, increased efficiencies and rates of carbonization, and improved final fibre properties. Control and acceleration of re-dehydration and cyclisation reactions promoted by the metals may be balanced by inhibition of complete carbon oxidation. Halogenated compounds (such as bromides and chlorides) are thought to inhibit complete oxidation and may act synergistically with metal oxides through activated precursors that can then undergo a catalysed dehydrogenation- aromatization reaction with minimal deep oxidation.
  • metal ion containing solutions such as FeCl 3 , N1NO 3 , C0SO 4 etc
  • post-formation treatments may also be carried out for enhancing the carbon bonding strength between the resin matrix (eg. PAN) and the NFC to obtain strengthened carbon fibres (1005).
  • the resin matrix eg. PAN
  • the NFC to obtain strengthened carbon fibres (1005).
  • a process (200) for producing carbon fibres in accordance with the present invention comprises an initial step of adding NFC with diameter of less than 50 nm with polymers such as lignin and/or polyethylene to form a polymerised nanocomposite melt.
  • Precursor fibres are subsequently obtained by melt spinning (220) of the nanocomposite melt.
  • the precursor fibres (230) may be further processed in accordance with a halogenation pre-treatment step 235.
  • the halogenation pre-treatment step may comprise forming a mixture of halogen material or a halogen derivative with the precursor fibre and heating the mixture to an elevated temperature.
  • a sample of the precursor fibre 230 may be mixed with a pre-determined quantity of liquid bromine to form a bromine-precursor fibre mixture.
  • the mixture may be introduced and sealed in a heat resistant quartz tube.
  • the contents of the quartz tube may then be subjected to an irradiation step involving irradiating the contents of the tube with simulated solar light.
  • Such an irradiation step promotes halogenation of the precursor fibre.
  • the halogenated precursor fibre is then collected after initially drying the halogenated precursor fibre and subsequently subjected to the processing steps 1001-1005 in accordance with the process described in the first embodiment to obtain carbon fibres.
  • a process (300) for producing carbon fibres in accordance with the present invention comprises an initial step of mixing NFC (with diameter of less than 50 nm) with water to form a colloidal dispersion in the form of a NFC hydrogel.
  • Precursor fibre filaments may be spun in an acetone coagulation bath by aqueous dope spinning of the NFC hydrogel.
  • the precursor fibres (330) may be further processed in accordance with the processing steps 1001-1005 in accordance with the process described in the first embodiment to obtain carbon fibres
  • Nanofibrillated cellulose (NFC) derived from spinifex grass with an average diameter of 3.7 ⁇ 1 nm and length of several microns was produced based on the high pressure homogenisation method described in the applicant's previously filed international patent application PCT/AU2014/050368 and incorporated herein by reference.
  • a homogeniser such as EmulsiFlex homogeniser or GEA homogenizer was used for homogenising the NFC.
  • Figure 4A illustrates a Transmission Electron Microscopy (TEM) image of the homogenised nanofibrillated cellulose (NFC) derived from spinifex grass before the carbonisation step.
  • NFC nanofibrillated cellulose
  • Figure 4B and 4C A 24 % residual mass was obtained after pyrolysis at 350 °C.
  • the carbonisation of the freeze dried spinifex NFC was also performed using a higher temperature carbonisation procedure, by stabilising the carbon fibre under air at 240 °C for 60 min then heating to 800 °C at a ramp rate of 5 °C/min followed by holding at 800 °C for 150 min under argon.
  • the measured residual mass was 10 %.
  • the quality of the resulting carbon was assessed based on the Raman spectra, as judged by the degree of disorder which is indicated by the 'D/G ratio' .
  • the peaks of the graphite structure-derived G-band and the defect-derived D-band appear in the vicinities of 1590 cm '1 and 1350 cm '1 , respectively as shown in Figure 5.
  • TGA results showed the onset degradation temperature to be about ⁇ 266°C for the cellulose nanofibrils (see Figure 7) whereas cellulose nanocrystals from commercial microcrystalline cellulose (MCC, Avicel PH 101 NF) showed decomposition temperature about ⁇ 330°C.
  • the catalyst (zinc oxide, 0.3 micron particles) had no significant effect on the lowering the thermal transition.
  • the low endotherm for plant derived cellulose nanofibrils can be related to the metal ions present in some plants which might be adsorbed as nutrients during their growth. As the ICP-OES analysis suggested, about 12 mg/kg of zinc was present in the nanofibrils.
  • This metal and other metal ions may act as a natural catalyst and possibly reduce the required amount of external catalyst. Such metal ions may also act as co-catalysts.
  • Fig 4C depicts a TEM image of a sample of the plant derived nanofibrils (with ZnO) pyrolised at 350°C for 30 minutes. The fibrillar structure is maintained in the carbon fibre.
  • the high aspect ratio of cellulose precursors is vital in (1) Forming percolating network between them, (2) Increased viscosity to facilitate the fibre-spinning (3) forming long pyrolysed carbon fibres.
  • FTIR Fourier Transformation Infrared
  • NFC suspension was obtained after homogenisation in accordance with the process described under example 1.
  • the suspension was freeze-dried by immersing in liquid nitrogen and drying under vacuum in a lyophiliser/freeze-drier in order to obtain dry lyophilizate or fluffy powder of NFC.
  • a thin sheet (paper) was produced from the NFC dispersion by vacuum filtering using a Biichner funnel fitted with a cellulose acetate membrane filter (pore size: 0.45 ⁇ , diameter: 47 mm. Advantec, Toyo Roshi Kaisha, Ltd, Japan). Prior to nitration, the dispersion was stirred for 24 hours, then filtration was continued until the wet sheet of NFC was formed.
  • NFC paper The wet sheet was peeled from the filter paper, placed between Teflon sheets and compression-moulded using a hydraulic press with no significant force at 103 °C for one hour, then the sample was removed and conditioned at room temperature and 65% humidity for a week prior to testing.
  • NFC paper the sheet of NFC will be referred to as "NFC paper”.
  • Figure 12 shows thermograms of the samples heated under nitrogen to 800 °C. It can be seen that spinifex nanofibrillated cellulose (NFC) exhibited higher residual mass (%) than others, at 18% on a mass basis.
  • NFC spinifex nanofibrillated cellulose
  • Table 2 compares the residual mass (%) values obtained from therm ogravimetry under nitrogen and carbonisation under air to 240 °C and then under argon to 800 °C. It can be seen that higher residual mass (%) was observed for sheets made from spinifex NFC. Table 2: Residual mass (%) from thermogravimetry and pyrolysis tests.
  • a weighed amount (40 mg) of NFC was taken into a quartz tube. Liquid bromine (about 1.1 mmol) was added and the tube was sealed with a Teflon coated rubber septum. The tube was then irradiated under a sun simulator (PLS-SXE300) at 120 °C for 1-2 h. Bromination was observed as a colour change from white to dark-red and then black for cellulose and from brown to black for lignin. These samples were then dried under vacuum at room temperature. To quantify bromination, the percentage weight increase was calculated with reference to the initial weight.
  • FIG. 9 shows the TGA thermogram for the halogen absorbed samples compared with neat spinifex NFC.
  • I-absorbed WMFP denotes iodine-absorbed Whatman filter paper
  • I-absorbed NFC denotes iodine-absorbed Spinifex nanofibrillated cellulose
  • Br-absorbed WMFP denotes bromine absorbed Whatman filter paper
  • Br-absorbed NFC denotes bromine-absorbed Spinifex nanofibrillated cellulose.
  • Figure 10 represents a visual comparison of various cellulosic materials before and after carbonation (240 °C under air 1 h and heated to 800 °C under argon at 5 °C/min ramp rate).
  • (1) denotes iodine-absorbed Whatman filter paper
  • (2) denotes iodine-absorbed spinifex NFC
  • (3) denotes bromine-absorbed Whatman filter paper
  • (4) denotes bromine-absorbed spinifex NFC.
  • the residual mass (%) with reference to initial amount of cellulose is listed in Table 3.
  • Kraft alkali lignin was purchased from Sigma Aldrich (Castle Hill, Australia) and used as received.
  • FIG. 1 1 compares the TGA thermograms of neat lignin and brominated lignin. An early stage weight loss (which began at around 200 °C) for brominated lignin may likely be related to the loss of bromine species such as HBr When normalised by the initial lignin mass, the residual mass is about 46 % which is similar to that of neat lignin at 43%. A similar observation was made when they were carbonised to 800 °C (see Figure 17 and Table 4). The D/G ratio calculated from Raman spectra was 1.20 for both lignin and brominated lignin.
  • [001 18] Wet spinning of PAN/fibre blends in a solvent such as DMF is known.
  • An amount of the nanocellulose fibrils obtained from Example 1 may be uniformly mixed with PAN in a solvent such as DMF to produce a PAN/nanocellulose blend fibre blend as precursor fibre filaments. It is expected that the addition of nanocellulose may result in improvement in the thermal stabilization of carbon fibres produced from such precursor fibres.
  • the amount of nanocellulose is variable and may be altered systematically in accordance with the properties as desired in the precursor fibre filament.
  • cellulose samples and PAN were vacuum-dried at 50 °C for 12 hours and PAN polymer was subsequently dissolved in dimethylformamide (DMF) at 50 °C by stirring.
  • DMF dimethylformamide
  • a dispersion of freeze-dried cellulose sample in DMF was stirred for 1.5 hours then subjected to ultrasonication at 20 % amplitude for three minutes (using the Q500 Sonicator). This procedure was repeated twice until a stable dispersion of nanoparticles in DMF was obtained.
  • the cellulose dispersion was subsequently added to the PAN polymer solution to give a final mass concentration of 1 wt% cellulose (relative to PAN mass) in the blend and these combined dispersions were then mixed by stirring for one hour at room temperature with a magnetic stirrer. To ensure a high level of mixing prior to
  • the composite solutions were mixed for a further three minutes with an ultrasonic probe at 20 % amplitude, followed by magnetic stirring for a further two hours at room temperature.
  • the electrospinning apparatus consisted of a syringe pump, syringe needle, high voltage power supply and a collector, which was fabricated using an aluminium foil strip. Each solution was loaded into a syringe and the positive electrode was clipped onto the syringe needle with 0.5 mm diameter. The flow rate of the PAN dispersions was held at 1.5 mm/hour, at an applied voltage of 20 kV and tip to collector distance of 13 cm, while the parameters for the PVA solutions were 0.5 mm/hour, 22 kV, and 13 cm respectively. In order to compare the effect of nanocellulose on the morphology and properties of polymer, a blank sample of each polymer was also electrospun as a control. Solutions were electrospun horizontally onto the target. After electrospinning, the collected composite nanofibers were dried in vacuum oven at 60 °C for 8 hours.
  • Samples of the electrospun precursor fibres were initially stabilized by heating to 240 °C in air at a rate of 3 °C/min, followed by a 60 minute isotherm at 240 °C.
  • the stabilized fibres were then carbonized by heating at a rate of 5 °C/min, followed by a 150 minute isotherm at the final temperature of 800 °C in an argon atmosphere.
  • Figure 18 compares the TGA thermograms of electrospun neat polyacrylonitrile, PAN composite fibres spun with 1 wt. % of different cellulose particles (MCC, CNC and NFC) and neat spinifex NFC.
  • nanofibrillated cellulose NFC represented as PAN/1 -NFC.
  • Figure 19 shows the PAN and PAN/cellulose composite fibers before and after carbonisation as listed under the column samples under Table 5.
  • Table 5 indicates the retained residual mass (%) with spinifex NFC than other cellulose after high temperature carbonisation.
  • Figure 20 shows the Raman spectra obtained from the carbonised fibres of PAN and
  • the D/G ratio for NFC incorporated PAN is significantly lower than for the others, at 1.20 compared to >1.4 for the PAN and PAN/CNC composite. It is possible that this is related to fusion induced by xylans in the hemicellulosic part of the NFC, as well as potentially the orientation of PAN molecules along the cellulose fibres facilitating crosslinking of sorts. Therefore, the addition of NFC may be improving the degree of order in PAN without affecting the yield.
  • Figure 21 compares the TGA thermograms of cast films of neat polyacrylonitrile PAN and its composite with 1.13 wt. % brominated spinifex nanofibrillated cellulose (where 1 wt. % accounts for NFC and 0.13 wt. % account for bromine in PAN). Bromination of the PAN/NFC film was carried out by the halogenation method described in previous examples including example 1. The presence of the brominated cellulose has resulted in a significant increase in mass yield after thermal treatment to 800 °C.
  • Figure 22 shows the cast films of PAN and PAN/brominated spinifex NFC before and after carbonisation. The retained mass (%) was calculated and is listed in Table 6.
  • An aqueous dispersion or suspension of the nanocellulose from example 1 may be prepared by suspending the nanocellulose fibrils in water to obtain a transparent
  • the suspensions may be spun in an acetone coagulation bath from a needle (such as ⁇ 0.95 mm) set on syringes (such as ⁇ 6.5 and35 mm). Different sizes of syringes may be used for control the spinning rate.
  • the syringes may be pushed by a syringe pump at rates of 2.3- 73.6 mm/min. Consequently, the spinning rates of the precursor fibre filaments may be controlled over the ranges of 0.1-100 and 0.1 -10 m/min, respectively.
  • Precursor fibre filaments as produced in any one of Examples 2-4 may be stabilised by heating and stretching the fibre filaments in a chamber with well controlled gas flow.
  • Stabilisation creates cross-linked "ladder polymer” chains and the T g of the fibre increases; the fibres are then carbonized ( ⁇ 800°C). This is followed by graphitization at temperatures ranging from 1 100°C to 3000°C while stretching to ensure a preferred crystalline orientation. Finally, post-formation treatments may also be carried out to enhance the carbon bonding strength between the epoxy resin matrix (PAN-Example 2 or PE-Example 3) and the nanocellulose.
  • the process may have rate limitations in the low temperature thermostabilization where the rate of fibre dehydration/dehydrogenation/oxidation is relatively slow (requiring residence times of up to 4 hours) and must be balanced against other processes.
  • Metal ion containing solutions such as FeCl 3 , NiN0 3 and CoS0 4 may also be used to treat the precursor fibres during the stabilization process. Without wishing to be bound by theory, it is hypothesized that addition of such ions may be associated with increased
  • halogenated compounds such as bromides and chlorides
  • the halogenated compounds can act synergistically with metal oxides through activated precursors that can then undergo a catalysed dehydrogenation-aromatization reaction with minimal deep oxidation.
  • the precursor fibres obtained from Examples 2 and 3 may be pre-treated with a number of specific metal cations found active in dehydropolycondensation reactions from several salts (halogen and non-halogen anions) including the transition metal cations (V + ; Cr++ ; Mn + ; Fe ++ ; Co + ; Ni ++ ; Cu + ).
  • nanoparticulate catalysts starting with known catalysts such as zinc and iron oxides and partially reduced compounds including doped and binary metal oxides, sulfides, and halides based on low cost hosts including iron, titanium, and manganese may also be added. These compounds may be in the form of nanoparticles with functionalized surfaces. Such catalysts may be impregnated or incorporated by preparatory methods such as ultrasonic spray pyrolysis and precipitation.

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  • Textile Engineering (AREA)
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Abstract

L'invention concerne un procédé de production de fibre de carbone, qui comprend les étapes consistant à : (a) filer des filaments de fibres précurseurs à partir d'une solution ou d'une dispersion comprenant des fibrilles de nanocellulose dont le diamètre est inférieur à 50 nm et un solvant ; et (b) à carboniser la fibre précurseur par pyrolyse à une température élevée pour obtenir la fibre de carbone.
PCT/AU2015/050074 2014-03-28 2015-02-24 Fibres de carbone obtenues à partir de matières premières biopolymères WO2015143497A1 (fr)

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WO2017060847A1 (fr) * 2015-10-08 2017-04-13 Stora Enso Oyj Processus pour la fabrication d'un corps façonné
WO2019026404A1 (fr) * 2017-08-04 2019-02-07 日本電信電話株式会社 Carbone de nanofibres de cellulose et procédé de production dudit carbone
CN109853086A (zh) * 2018-11-08 2019-06-07 大连工业大学 一种木质素/醋酸纤维素基静电纺丝碳纤维及其制备方法与应用
JPWO2021106067A1 (fr) * 2019-11-26 2021-06-03
CN113943984A (zh) * 2021-09-09 2022-01-18 中国船舶重工集团公司第七二五研究所 一种生物质基碳纤维电磁吸收材料的制备方法
CN114150435A (zh) * 2021-12-06 2022-03-08 东北林业大学 一种静电纺纳米复合纤维膜及其制备方法

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CN108138381A (zh) * 2015-10-08 2018-06-08 斯道拉恩索公司 一种制造成形体的方法
WO2017060847A1 (fr) * 2015-10-08 2017-04-13 Stora Enso Oyj Processus pour la fabrication d'un corps façonné
TWI719066B (zh) * 2015-10-08 2021-02-21 芬蘭商史託拉安索公司 製造成形體的方法
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WO2019026404A1 (fr) * 2017-08-04 2019-02-07 日本電信電話株式会社 Carbone de nanofibres de cellulose et procédé de production dudit carbone
JPWO2019026404A1 (ja) * 2017-08-04 2020-07-27 日本電信電話株式会社 セルロースナノファイバーカーボンとその製造方法
CN109853086A (zh) * 2018-11-08 2019-06-07 大连工业大学 一种木质素/醋酸纤维素基静电纺丝碳纤维及其制备方法与应用
CN109853086B (zh) * 2018-11-08 2021-09-03 大连工业大学 一种木质素/醋酸纤维素基静电纺丝碳纤维及其制备方法与应用
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CN113943984A (zh) * 2021-09-09 2022-01-18 中国船舶重工集团公司第七二五研究所 一种生物质基碳纤维电磁吸收材料的制备方法
CN113943984B (zh) * 2021-09-09 2023-09-26 中国船舶重工集团公司第七二五研究所 一种生物质基碳纤维电磁吸收材料的制备方法
CN114150435A (zh) * 2021-12-06 2022-03-08 东北林业大学 一种静电纺纳米复合纤维膜及其制备方法

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