WO2018065335A2 - Minéralisation du bois et de matières cellulosiques - Google Patents

Minéralisation du bois et de matières cellulosiques Download PDF

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Publication number
WO2018065335A2
WO2018065335A2 PCT/EP2017/074899 EP2017074899W WO2018065335A2 WO 2018065335 A2 WO2018065335 A2 WO 2018065335A2 EP 2017074899 W EP2017074899 W EP 2017074899W WO 2018065335 A2 WO2018065335 A2 WO 2018065335A2
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Prior art keywords
wood
impregnation
cellulosic material
wooden
wooden material
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WO2018065335A3 (fr
Inventor
Thomas Volkmer
Frédéric PICHLIN
Raphael Stephan GYR
Patrick KAISER
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Berner Fachhochschule Architektur Holz und Bau BFH AHB
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Berner Fachhochschule Architektur Holz und Bau BFH AHB
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Priority to EP17786839.5A priority Critical patent/EP3519147B1/fr
Publication of WO2018065335A2 publication Critical patent/WO2018065335A2/fr
Publication of WO2018065335A3 publication Critical patent/WO2018065335A3/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0207—Pretreatment of wood before impregnation
    • B27K3/0214—Drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0271—Vapour phase impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/02—Processes; Apparatus
    • B27K3/0278—Processes; Apparatus involving an additional treatment during or after impregnation
    • B27K3/0292—Processes; Apparatus involving an additional treatment during or after impregnation for improving fixation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/18—Compounds of alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/007—Treating of wood not provided for in groups B27K1/00, B27K3/00 using pressure
    • B27K5/008—Supercritical or high pressure fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
    • B27K5/04—Combined bleaching or impregnating and drying of wood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing

Definitions

  • the invention relates to a method for producing a mineralized wood or mineralized cellulosic materials.
  • the invention relates to mineralized wood , wooden material and other cellulosic material suitable for indoor and outdoor use and methods for making such materials.
  • Various attempts have been heretofore made to protect wood , wooden material and other cellulosic material against fungi and to improve its fire resistance/reaction to fire.
  • the known products can be divided into three groups: i) water based salts, ii ) solvent based formulations, and iii ) creosotes.
  • water solved metal salts are not stable in wood and are therefore only used for indoor applications. Apart from some essential additives they consist of 80- 1 00% of the active agent. They are easily washed out and already after one rain fall, the whole effect of the substance can be lost if the application was done by brushing or dipping.
  • the main substances are fluoride, silicate or borate.
  • the different salt formulations can further be differentiated by the solubility and penetration behavior.
  • chrome salts For outdoor uses the above mentioned salt formulations need to be fixed with chrome. Within 4-6 weeks after the application chrome salts react with certain wood components. Thereby leaching can be significantly reduced.
  • the fixation of chrome salts in wood is based on the reduction of chrome (VI ) to chrome ( I I I ). With chrome ( I I I ) the fluorine or copper salts react to insoluble chemical combinations and become very weather resistant. Parallel to the fixation of the salts the color of the wood changes as well from yellow-orange to olive-green.
  • the chrome functions mainly as fixing agent. Certain chrome compounds (chrome (VI ), for example zinc chromate) are very toxic to animals and humans.
  • salt formulations provide additional protection against soft rot.
  • These salts can be used for impregnation of wood in very wet conditions and in soil contact.
  • the expected rates of leaching for copper-chrome combinations are about 5 % .
  • Common water soluble metal salts are: Chrome-fluoride-salts, Chrome-fluoride-boron-salts, Chrome-copper-salts, Chrome- copper-boron salts and Chrome-copper-fluoride salts.
  • creosotes are restricted to special applications.
  • Railway sleepers represent the main field for impregnation with creosotes.
  • the efficiency of the creosotes depends on their composition . Products with high concentrations of polycyclic aromatic compounds with 4-6 rings show the best efficiency.
  • a coating of creosote treated wood is not possible. Depending on certain circumstances creosotes can migrate and pollute the surface. Creosote impregnated parts need to be treated as hazardous waste after their lifetime.
  • Solvent based preservative formulations are used for indoor and outdoor applications with no ground contact.
  • the common fields of application are usually class of utilization 1 - 3 (regarding EN 335, for example class 3 windows and doors).
  • the basic components are organic solvents, biocide active substances, binders and pigments. These products are mainly water stable and can not be leached out but they do not show the necessary performance in earth contact.
  • the concentration of the active substances is normally between 0.5 - 5 % because they are highly efficient.
  • the active agents in solvent based preservatives belong to the same groups like the biocide agents in herbicides, but they differ in certain points significantly.
  • a treatment with these substances results in delayed ignition , reduced heat release rate and slower spread of flames. They act on different levels, most of the time combined : promotion of char formation at lower temperature than wood usually degrades, free- radicals trapping in the flame, dilution of combustible gases coming from wood with non- combustible gases, reduction of heat content of the volatile gases, or coating protection of the wood surface.
  • the most commonly used fire retardants for wood products are inorganic salts, of which some can absorb moisture promoting decay and destruction of metal joints. Because these salts are typically water soluble and easily leached out of wood, water-insoluble organic fire retardants have been developed, which are mainly based on amino resin systems polymerized after impregnation into wood [2].
  • fire retardants despite reducing the combustion potential of wood, can also unfavorably affect following properties of wood: mechanical strength, hygroscopicity, stability, toxicity, adhesive and mechanical properties, and receptivity to coatings. Moreover, they are used in relatively large doses, which impacts the cost of the structure. The smoke emissions, together with carbon monoxide increased concentration during fire might happen as well, as it is the case with the widely used monoammonium phosphate [4]. Intumescent coatings are easier to apply and less costly but their susceptibility to cracks, abrasion and wear results in the loss of efficiency.
  • the purpose of this invention is to provide a method for protecting wood, wooden material and other cellulosic material by mineralization . Due to the novel mineralization method, the water soluble reactants penetrate the material stepwise and water insoluble salts, preferably in crystalline form, are generated in situ within the cells themselves, in the cell walls, in the pits and in the middle lamellas.
  • a further purpose of this invention is to provide mineralized products, i.e. wood, wooden material and other cellulosic material, in such a way as to allow their intended functions while also providing one or more of the following properties or functions: i) protection against fungi, ii ) improving their biological resistance, iii ) improving moisture and weather resistance, iv) reducing flammability, v) improved fire resistance.
  • the purpose of this invention is to provide an improved method for mineralization of wood, wooden material, for example materials containing wood, such as windows, tables and doors, and other cellulosic material, the method comprising: i) a first impregnation step, comprising a first impregnation of wood, wooden material or other cellulosic material with an aqueous solution of potassium methyl siliconate or potassium oxalate, ii) a first drying step, comprising drying of the wood, wooden material or other cellulosic material, iii ) a second impregnation step, comprising a second impregnation of wood, wooden material or other cellulosic material with an aqueous solution of calcium chloride or C0 2 (gaseous or fluidic) and iv) a second drying step, comprising drying of the wood , wooden material or other cellulosic material.
  • the concentration of potassium methyl siliconate or potassium oxalate dissolved in the solution is 1 00% of their saturation concentration .
  • the concentration of calcium chloride dissolved in the solution may be 1 00% of its saturation concentration .
  • the first and/or the second impregnation comprises a phase of overpressure during which the pressure is selected in the range of 5 - 1 0x 1 0 5 Pa ( 5- 1 0 bar) and the temperature in the range of 1 5 to 50°C.
  • the duration of the phase of overpressure in the first and/or the second impregnation step is ⁇ 1 hour, typically 1 - 24 h, preferably 4-8 h .
  • the first and/or the second impregnation is preceded by a vacuum phase, during which the wood , wooden material or other cellulosic material is exposed to underpressure, preferably for 30 minutes at 40 to 60 °C and preferably to an underpressure of 1 - 3x 1 0 4 Pa ( 1 00-300 mbar).
  • the wood, wooden material or other cellulosic material is dried above the fiber saturation level of 28-35 %, preferably 30% in the first drying step.
  • a fiber saturation level of 1 00% is the point in the drying process at which only water bound in the cell walls remains and all other water having been removed from the cell cavities.
  • the first drying step comprises preferably a vacuum phase, during which the wood, wooden material or other cellulosic material is exposed to underpressure, preferably for 30 minutes at 40 to 60 °C and preferably at an underpressure of 1 - 3x 1 0 4 Pa ( 1 00-300 mbar).
  • the wood , wooden material or other cellulosic material is dried to a wood moisture, preferably a wood moisture of 1 2 to 1 6 % in the second drying step.
  • the wood moisture is calculated by the formula (m s -md)/md * 1 00, wherein m s is the mass of the sample and irid is the mass of the sample after drying in an oven at 1 03 °C until mass constancy.
  • Wood, wooden material or other cellulosic material which is mineralized in a method according to the present invention is characterized in that calcium methyl siliconate or calcium oxalate or polymethyl silicic acid of low or no solubility in water is deposited in the wood, wooden material or other cellulosic material, preferably in crystalline form.
  • the untreated wood, wooden material or other cellulosic material gains 30 - 40% weight by mineralization with calcium methyl siliconate, 40 - 50 %, by mineralization with calcium oxalate and 20-30% by mineralization with polymethyl silicic acid.
  • the mineralization with calcium methyl siliconate is also based on two impregnation steps.
  • the material is impregnated in an aqueous solution with potassium methyl siliconate CH 3 Si (OH ) 2 OK.
  • the material is dried and then impregnated with calcium chloride CaCI 2 (cation ) in aqueous solution .
  • the potassium methyl siliconate already present as anion in the material to be mineralized and the calcium chloride provided in the second impregnation step form calcium methyl siliconate ⁇ [CH 3 Si (OH )20]2Ca ⁇ S oiid, preferably in crystalline form, which is practically not soluble in water, and KCI.
  • the molar ratio between both reactive compounds is 2: 1 .
  • the reactive compounds preferably solutions of 2: 1 molar content are prepared.
  • the molecular weight of CH 3 Si (OH ) 2 OK is 1 32.23 g/mol, the water solubility 51 .5 g/ 1 OOg H 2 0.
  • the molecular weight of CaCI 2 « 6H 2 0 is 21 9.08 g/mol, the water solubility 81 .3 g/ 1 00g H 2 0.
  • 1 solutions 587. 1 0 g potassium methyl siliconate is dissolved per 1 L H 2 0 and 485.5 g calcium chloride per 1 L H 2 0.
  • the mineralization with calcium oxalate is also based on two impregnation steps.
  • the material is impregnated in an aqueous solution with potassium oxalate C 2 0 4 K 2 .
  • the material is dried and then impregnated with calcium chloride CaCI 2 (cation ).
  • the potassium oxalate already present as anion in the material to be mineralized and the calcium chloride form calcium oxalate ⁇ C 2 0 4 Ca ⁇ SO iid, preferably in crystalline form, which is practically not soluble in water, and KCI.
  • the molar ratio between both reactive compounds is 1 : 1 .
  • a solution of equimolar content is prepared.
  • the molecular weight of C 2 0 4 K 2 - H 2 0 is 1 84.23 g/mol, the water solubility 38.7 g/ 1 00g H 2 0.
  • the molecular weight of CaCI 2 - 6H 2 0 is 21 9.08 g/mol, the water solubility 81 .3 g/ 1 00g H 2 0.
  • 387 g potassium oxalate is dissolved per 1 L H 2 0 and 460 g calcium chloride per 1 L H 2 0.
  • the mineralization with polymethyl silicic acid is also based on two impregnation steps.
  • the material is impregnated in an aqueous solution with potassium methyl siliconate CH 3 Si (OH ) 2 OK.
  • the material is impregnated with C0 2 either in the fluidic or the gaseous state.
  • the potassium methyl siliconate already present as anion in the material to be mineralized and the C0 2 provided in the second impregnation step form polymethyl silicic acid ⁇ [CH 3 Si (OH ) 2 0-] n ⁇ soiid, which is practically not soluble in water, and K 2 C0 3 .
  • CaCI 2 Calcium chloride
  • CaCI 2 is an ionic halide in solid state at room temperature.
  • CaCI 2 is a hygroscopic compound and forms solutions in water dissociating in calcium and chloride ions. It can be commercially found in pure state, but more commonly as hyd rated compound for example as mentioned above as CaCI 2 - 6H 2 0, or as CaCI 2 -4H 2 0, CaCI 2 - 2 H 2 O or CaCI 2 - H 2 0. Properties will evidently depend on its hydration degree. For the tests performed CaCI 2 - 6H 2 0 was employed .
  • Potassium oxalate is a salt of oxalic acid. Its appearance is that of transparent and colorless crystals. In aqueous solutions it can dissociate to form oxalate and potassium ions. Oxalate ions can be combined with calcium, magnesium, and iron ions to form less water-soluble or insoluble salts. Potassium oxalate is commercially available as anhydrous and monohydrate salt. In the current experiments, the monohydrate (C 2 0 4 K 2 - H 2 0) was used . Once the oxalate anion has reacted with the cation from the calcium chloride solution it forms an insoluble salt (C 2 0 4 Ca ) that is retained in wood, providing the protection effect.
  • Potassium methyl siliconate (CH 3 Si (OH ) 2 OK) Potassium methyl siliconate is commercially available as an aqueous solution and it is commonly used in diluted form for water-repellent applications. Aqueous solutions may be highly alkaline and therefore care must be taken during handling .
  • Wood, wooden material and other cellulosic material are used as wood, wooden material and other cellulosic material.
  • Beech Fagus sylvatica
  • pine Pinus sylvestris
  • Beech Fagus sylvatica
  • beech is a hardwood belonging to the division of angiosperms. As it is characteristic for hardwoods, beech is composed by vessel elements, fibers (tracheids), parenchyma and ray cells.
  • Vessels are arranged in a non -specific pattern , resulting in a semi-porous to diffuse porous distribution. Growth ring limits are demarked by dark colored late wood . Density varies from 0.48 - 0.68 - 0.88 g/cm 3 .
  • Pine Pinus sylvestris
  • Pine is a softwood belonging to the division of conifers. Pine is mainly composed by tracheids, as is characteristic for softwoods and has well differentiated thick walls in late wood and thin walls in early wood. Density varies from 0.3 - 0.49 - 0.86 g/cm 3 (in the early zone).
  • wood preferably used in the method according to the invention are: silver fir, maple, cotton wood and alder.
  • Wood which fulfils the requirements for wood according to the norm EN 1 1 3 is preferably used and mineralized in the method according to the present invention .
  • the main requirements of the norm EN 1 1 3 are: a ) Wood quality: wood should have straig ht grains and no knots. Pine should be exclusively of sapwood and poor in resin . Beech should not have red heart. b) The number of annual rings in the width direction must be 2.5 - 8 per cm for pine, and 2 - 6 per cm for beech. c) The direction of the rings in the cross section could have any direction but should not be tangential to the width direction of the cross section . d ) The proportion of latewood in the cross section should not be more than
  • specimens need to be completely covered and weights need to be added to avoid samples to float.
  • c) First, specimens submerged into the deionized water bath undergo a vacuum (40 mbar) during 20 min. Then, they stay at atmospheric pressure during 2 hours. Afterwards this first water bath is poured and changed .
  • the biological tests were done on the basis of the European Standard EN 1 1 3 ( European Standard , 1 996 ) with some modifications in order to allow accelerated tests. Two series of biological tests have been carried out in order to evaluate the resistance of the mineralized woods, wooden materials and other cellulosic materials against fungi and biological deg radation .
  • Fungi used in the tests were Coniophora souna, Coriolus versicolore and Poria placenta .
  • the weight loss percentages of mineralized samples was determined after attack with different fungi according to EN 1 1 3 and before leaching .
  • the fire tests were performed according to EN ISO 1 1 925- 2.
  • the samples are placed vertically into the holding device and the burner is installed in front of the sample tilted 45°.
  • the distance of the burner from the unprotected edge of the sample is 1 6mm.
  • the flame has a length of 20mm.
  • Fig. 1 shows a schematic flow chart of the mineralization method according to the present invention
  • Fig. 2 shows a schematic flow chart of an preferred embodiment of the mineralization method according to the present invention comprising vacuum phases preceding the first and the second impregnation ;
  • Fig. 3 compares the solid content of Pine and Beech samples treated by methods T1 , T2 and T3 before and after leaching, (T1 calcium oxalate, T2 calcium methylsiliconate,
  • Fig. 4 shows the weight loss of samples mineralized with calcium oxalate and control samples after exposure to fungi (following EN 1 1 3 ) before leaching , illustrating a clear trend showing that impregnated samples provide a protection effect of wood against fungi attack. Furthermore, Fig, 4 shows that Coniophora souna cultures are more active than Coriolus versicolor cultures.
  • P-T1 -CN Pine Calcium oxalate Coniophora quina
  • P-T1 -CR Pine Calcium oxalate Coriolus versicolor
  • B-T1 - CN Beech Calcium oxalate Coniophora liena
  • B-T1 -CR Beech Calcium oxalate Coriolus versicolor
  • Fig. 5 shows the weight loss of samples mineralized with Calcium methyl siliconate and control samples after exposure to fungi (following EN 1 1 3 ) before leaching .
  • Fig. 5 illustrates a clear trend showing that impregnated samples provide a significant protection effect of wood against fungi attack.
  • Fig 6 shows burn ing time after removal of the flame for different mineralized wood samples of fir and beech, following EN ISO 1 1 925- 2 (treatment 1 calcium oxalate, treatment 2 Calcium methyl siliconate, treatment 3 polymethyl silicic acid ). As can be seen , all treatments 1 -3 significantly improve the fire resistance of the wooden samples;
  • Fig. 7 to Fig. 1 1 show pine and beech samples mineralized with Calcium methyl siliconate and Calcium oxalate and polymethyl silicic acid .
  • Fig 7 shows REM images of an untreated reference beech sample before (a ) and after
  • Fig 8 shows REM images of beech treated with calcium chloride and potassium oxalate after leaching for 9 days and boiling for 4 hours ( 1 1 7°C).
  • Calcium oxalate crystals are produced in the lumen of the cells. Mainly the vessels are filled with calcium oxalate (a, c), but also in the lumen of the fibers and parenchyma cells (b) Oxalate crystals are present.
  • the reaction product not always fills the whole cell lumen but it covers the cell wall surface (a, d ).
  • Fig 9 shows REM images of pine treated with calcium chloride and Potassium oxalate after leaching for 9 days.
  • the oxalate crystals can be detected in the late and early wood tracheids (a,b). Mainly the cell walls (e) are covered but sometimes the whole lumen is filled (c,d). A high concentration of reaction product is present in the bordered pits (f ).
  • Figure 9 demonstrates that the impregnation takes place in the whole sample and in almost every cell.
  • Fig 1 0 shows REM images of beech treated with calcium chloride and potassium methyl siliconate after leaching for 9 days and boiling 4 hours ( 1 1 7°C).
  • the lumen of the cells and the fibers are filled , the crystals form a solid bloc (a, b).
  • the cell wall layer is also infiltrated and intensively covered with the reaction product (c (leached and boiled ), d (only leached ) ).
  • the cavities of the radial parenchyma cells are less filled in comparison to the bigger lumen of the vessels (e).
  • Fig 1 1 shows REM images of pine treated with calcium chloride and potassium methyl siliconate after leaching for 9 days. Siliconates are visible in the early and late wood tracheids (a ). Some of the cells are completely filled with the siliconate crystals ( b) and sometimes the cell wall is covered by a layer of these crystals (e). The membranes of the bordered pits are often infiltrated and mineralized by the impregnation products (c, d ) .
  • the following parag raph describes the process steps of mineralization at an industrial level for facade claddings according to one embodiment of the present invention .
  • the procedure can be applied for the mineralization with calcium oxalate and calcium methyl siliconate.
  • the industrial application of this specific mineralization will be done in two autoclaves with systems to monitor the vacuum-pressure cycle.
  • the following parag raph describes the process steps of mineralization at an industrial level for facade claddings according to a further embodiment of the invention .
  • the procedure can be applied for the mineralization with polymethyl silicic acid.
  • the industrial application of the mineralization will be done in one autoclave with a system to monitor the vacuum- pressure cycle.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

L'invention concerne un procédé permettant de minéraliser le bois, les matériaux en bois et autres matières cellulosiques comprenant : i) une première étape d'imprégnation consistant à imprégner le bois, les matériaux en bois et autres matières cellulosiques avec une solution aqueuse de méthylsiliconate de potassium ou d'oxalate de potassium, ii) une première étape de séchage consistant à sécher le bois, le matériaux en bois et autres matières cellulosiques, iii) une seconde étape d'imprégnation consistant à imprégner le bois, les matériaux en bois et autres matières cellulosiques avec une solution aqueuse de chlorure de calcium ou C02 (gazeux ou fluidique), et iv) une seconde étape de séchage consistant à sécher le bois, les matériaux en bois et autres matières cellulosiques. Le procédé de minéralisation selon l'invention permet aux produits insolubles dans l'eau des étapes d'imprégnation de pénétrer le matériau en profondeur et sont générés in situ dans les cellules mêmes, dans les parois cellulaires et les cavités et entre les cellules de xylème (essentiellement les fibres et les scléréides). Les produits minéralisés sont protégés des champignons, leur résistance biologique est supérieure, ainsi que leur résistance à l'humidité et aux intempéries, et ils sont moins inflammables. Les produits ne sont pas toxiques et ne présentent aucun danger pour l'environnement.
PCT/EP2017/074899 2016-10-03 2017-09-29 Minéralisation du bois et de matières cellulosiques Ceased WO2018065335A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP17786839.5A EP3519147B1 (fr) 2016-10-03 2017-09-29 Minéralisation du bois et de matières cellulosiques

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH01307/16 2016-10-03
CH13072016 2016-10-03

Publications (2)

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WO2018065335A2 true WO2018065335A2 (fr) 2018-04-12
WO2018065335A3 WO2018065335A3 (fr) 2018-05-17

Family

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Family Applications (1)

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PCT/EP2017/074899 Ceased WO2018065335A2 (fr) 2016-10-03 2017-09-29 Minéralisation du bois et de matières cellulosiques

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Country Link
EP (1) EP3519147B1 (fr)
WO (1) WO2018065335A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201900011652A1 (it) 2019-07-12 2021-01-12 Eng Consulting Promotion Sagl Processo per la mineralizzazione di legno e legno mineralizzato così ottenuto
BE1028001B1 (fr) * 2020-01-20 2021-08-16 Centre Dimpregnation Des Bois De Belgique Procede de traitement preventif de bois
EP3900902A1 (fr) * 2020-04-23 2021-10-27 Imprägnierwerk AG Willisau Minéralisation du bois ou de matériau en bois à l'aide d'acétate de calcium

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Publication number Priority date Publication date Assignee Title
GB191306179A (en) * 1913-03-12 1913-10-23 Louis Dautreppe Improved Process and Apparatus for Impregnating Wood.
SU1541056A1 (ru) * 1987-12-30 1990-02-07 Белорусский технологический институт им.С.М.Кирова Способ получени огнестойкой древесины
JP3919395B2 (ja) * 1999-04-22 2007-05-23 道夫 加島 改質木材の製造方法
DE10062984A1 (de) * 2000-12-16 2002-06-20 Nutrinova Gmbh Holz mit fixierter Sorbinsäure oder Sorbinsäuresalzen
US6649569B2 (en) * 2001-01-12 2003-11-18 Jacques Vionnet Composition intended for the protection of a solid substrate and its use
EP2937193A1 (fr) * 2014-04-24 2015-10-28 ETH Zurich Matériaux en bois minéralisés et procédés fournissant des matériaux en bois minéralisés

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT201900011652A1 (it) 2019-07-12 2021-01-12 Eng Consulting Promotion Sagl Processo per la mineralizzazione di legno e legno mineralizzato così ottenuto
BE1028001B1 (fr) * 2020-01-20 2021-08-16 Centre Dimpregnation Des Bois De Belgique Procede de traitement preventif de bois
EP3851261A3 (fr) * 2020-01-20 2021-09-08 Centre d'Imprégnation des Bois de Belgique SPRL Procede de traitement preventif de bois
EP3900902A1 (fr) * 2020-04-23 2021-10-27 Imprägnierwerk AG Willisau Minéralisation du bois ou de matériau en bois à l'aide d'acétate de calcium

Also Published As

Publication number Publication date
WO2018065335A3 (fr) 2018-05-17
EP3519147A2 (fr) 2019-08-07
EP3519147B1 (fr) 2021-10-27

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