US20210122902A1 - Transparent wood composite, systems and method of fabrication - Google Patents

Transparent wood composite, systems and method of fabrication Download PDF

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Publication number
US20210122902A1
US20210122902A1 US16/074,148 US201716074148A US2021122902A1 US 20210122902 A1 US20210122902 A1 US 20210122902A1 US 201716074148 A US201716074148 A US 201716074148A US 2021122902 A1 US2021122902 A1 US 2021122902A1
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Prior art keywords
wood
transparent
cellulose
lignin
natural
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Abandoned
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US16/074,148
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English (en)
Inventor
Liangbing Hu
Mingwei Zhu
Tian Li
Amy S. Gong
Jianwei SONG
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University of Maryland at College Park
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University of Maryland at College Park
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Priority to US16/074,148 priority Critical patent/US20210122902A1/en
Assigned to UNIVERSITY OF MARYLAND, COLLEGE PARK reassignment UNIVERSITY OF MARYLAND, COLLEGE PARK ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ZHU, MINGWEI, HU, LIANGBING, GONG, Amy, SONG, Jianwei, LI, Tian
Publication of US20210122902A1 publication Critical patent/US20210122902A1/en
Abandoned legal-status Critical Current

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    • B32B27/40Layered products comprising a layer of synthetic resin comprising polyurethanes
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    • H01L31/02Details
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    • H01L31/02161Coatings for devices characterised by at least one potential jump barrier or surface barrier
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    • H01L31/02168Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells the coatings being antireflective or having enhancing optical properties for the solar cells
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    • H01L31/0248Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264Inorganic materials
    • H01L31/0304Inorganic materials including, apart from doping materials or other impurities, only AIIIBV compounds
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    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/184Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIIBV compounds, e.g. GaAs, InP
    • BPERFORMING OPERATIONS; TRANSPORTING
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Definitions

  • the present invention is directed to light transmitting systems, and in particular to wood-based light transmitting systems.
  • the present invention is directed to anisotropic transparent wood mesoporous composites having unique optical properties in a broad wavelength range between 400 nm and 1100 nm which can be utilizable for a wide range of optoelectronic and photonic systems, where light management is crucial for enhanced operation efficiency.
  • the systems provide for high mechanical strength and ductility and may be used as energy efficient building materials for guided sunlight transmittance and effective thermal insulation.
  • the present invention is also directed to a method of fabrication of transparent wood composites in a two stage process, including extraction of lignin from low tortuosity channels of the natural wood (in the first stage) followed by the second stage for infiltrating of lignin-devoid wood blocks with material(s) having refractive index substantially matching the refractive index of the channel walls' cellulose-containing material.
  • the present invention is directed to optoelectronic systems using a broad range light management layer formed with anisotropic transparent wood composite(s) fabricated in a cost-efficient manner.
  • the present invention is further directed to energy efficient building materials for guided sunlight transmittance and effective thermal insulation using transparent wood composites which, when installed as a replacement of windows and/or rooftops, efficiently harness light for consistent and uniform indoor lighting.
  • Wood is a widely used structural material that has excellent mechanical properties due to the unique structures developed during its natural growth. Depending on their types and geographical differences, different woods display a wide variety of mesostructures. For example, soft woods typically have a more porous structure due to their fast growth. Hard woods normally have a more dense structure and a higher density compared to soft wood. Although the large-scale structures in different woods can be dramatically different, the mesoporous structures of wood share similarities in their hierarchical structures.
  • Typical wood is mainly composed of cellulose and hemicellulose fibers, and lignin.
  • Wood cell nano- and micro-fibers are naturally aligned along the growth direction and form walls of the internal channels.
  • the fibers' dimensions are typically from 3 mm to 5 mm in length and from less than 10 ⁇ m to 50 ⁇ m in diameter.
  • the alignment of cellulose nanofibers together with the strong interactions among the biopolymers in wood is enhanced by lignin which acts as a matrix adhesive, forming a typical fiber reinforced, anisotropic mesostructure.
  • Each wood cell fiber contains multiple microfibers and each microfiber can further be broken down into nanosized fibers.
  • Wood is either directly used as a structural material or as the rich source from which cellulose microfibers are extracted to make non-transparent paper, which is used widely in everyday life.
  • CNF cellulose nanofibers
  • CNC cellulose nanocrystals
  • CNF and CNC are extremely attractive for a broad range of new applications including green electronics, energy storage and biological devices.
  • lignin which is a byproduct of the pulping process, has been explored as a potential low cost material for making high-performance carbon or energy storage electrodes.
  • Natural wood is not transparent for mainly two reasons. First, natural wood has microsized channels that scatter light in the visible range. Second, lignin infiltrating wood (up to 30% by mass) absorbs visible light and leads to the opaque appearance of most woods.
  • Light management is critical for improving the optoelectronic devices.
  • a range of light trapping strategies have been developed, such as nano-cone structures, nano-dome arrays, nano-tube lattices, nanowires, as well as metallic nanoparticles, which increase the light transport path in the active layers to effectively increase energy conversion efficiencies in devices.
  • Bio-inspired approaches have also been used to design advanced nanostructures for light trapping.
  • Transparent optical material is one of the most important building blocks for solar-based energy conversion devices, where glass has long been the traditional material.
  • plastic has been explored with success as a glass replacement for optical device integrations.
  • plastic substrates have intrinsic problems such as poor thermal stability, difficulty in being functionalized, and adding waste to landfills.
  • Mesoporous wood fibers in nature directed to photonics is desirable due to its abundance, unique hierarchical structure, rich surface chemistry and use of well-developed processing of wood.
  • wood has unique mesostructures that can lead to advantageous properties such as excellent mechanical strength and efficient transport of water and ions.
  • wood In contrast to glass, wood is a natural thermal insulator with excellent mechanical strength, which has been used as a structural material for houses and cabins for thousands of years. It is the hierarchical structure and the strong interactions among cellulose, hemicellulose and lignin that leads to excellent mechanical properties in wood.
  • natural wood is not transparent due to light absorbing lignin and microsized scattering cell lumens.
  • wood could be fabricated in a manner to make it transparent, it would find its usefulness in a wide range of applications from everyday uses (such as, for example, wood furniture) to more advanced applications (such as structural materials in automobiles, as building materials, and in optoelectronics, etc.).
  • Transparent wood composites have been fabricated for the first time by the novel two-stage fabrication process by removing lignin from a wood block pre-cut from natural block, followed by infiltrating the lignin-devoid wood block with index-matching polymer(s) to achieve high optical transparency of the wood block.
  • different types of transparent wood composite material can be fabricated where the natural internal channels in wood align either perpendicularly to the wood cut plane, or along the wood cut plane, or in other angled relationships therebetween.
  • the structure-process-properties relationship has been studied in two types of the subject wood composites, and it was found that the fabrication processes for the cross-cut and longitudinally cut wood samples require different fabrication regimes due to the distinct kinetics of the lignin removal and polymer infiltration along the open internal channels in the cross-cut and longitudinally-cut samples.
  • the resulting wood composites maintain the original alignment structure of cellulose inside the cell (channels) walls and display extraordinary anisotropic optical and mechanical properties.
  • the present invention is directed to a transparent wood composite which comprises:
  • a wood block of predetermined dimensions pre-cut from a natural wood in a predetermined angular relationship to a direction of natural internal channels of the natural wood and treated to remove therefrom the natural wood's lignin
  • a filling polymer having refractive index substantially matching the refractive index of the cellulose-containing material of the internal channels' walls, and substantially completely infiltrating the internal channels of the lignin-devoid wood block.
  • the pre-cut wood block is configured with an upper and a bottom cut planes spaced apart one from another a pre-determined distance of 100 ⁇ m or larger, for example, ranging approximately between 100 ⁇ m and 1.4 cm for different applications. At least one of the upper and bottom cut planes extends in crossing relationship with the natural internal channels or substantially therealong, or in other angular relationship therebetween.
  • the filling polymer may be selected from a large group of materials including:
  • Thermosetting polymers such as, for example, Polyester fiberglass, Polyurethanes polymers, Vulcanized rubber, Bakelite, Duroplast, Urea-formaldehyde, Melamine resin, Diallyl-phthalate (DAP), Polyimides and Bismaleimides, Cyanate esters or polycyanurates, Furan resins, Polyester resins, Silicone resins, Benzoxazine resins, Bis-Maleimides (BMI), Cyanate ester resins, Epoxy (Epoxide) resins, Phenolic (PF) resins, Polyester resins, Polyimides, Polyurethane (PUR) resins, Silicone Resins, Vinyl ester resins,
  • Polyester fiberglass Polyurethanes polymers
  • Vulcanized rubber Bakelite, Duroplast, Urea-formaldehyde
  • Melamine resin Diallyl-phthalate (DAP)
  • DAP Diallyl-phthalate
  • Polyimides and Bismaleimides Cyanate esters or polycyanur
  • Thermoplastic polymers such as, for example, Acrylic, ABS, Nylon, PLA, Polybenzimidazole, Polycarbonate, Polyether sulfone, Polyetherether ketone, Polyetherimide, Polyethylene, Polyphenylene oxide, Polyphenylene sulfide, Polypropylene, Polystyrene, Polyvinyl chloride, Teflon,
  • Cellulose derivatives such as, for example, Cellulose acetate, Cellulose acetate butyrate, Cellulose triacetate, Methyl cellulose, Hydroxypropyl methyl cellulose, Ethyl cellulose, Hydroxyethyl cellulose, Carboxymethyl cellulose, Dissolved cellulose, Nanofibrillated cellulose, Cellulose nanocrystals,
  • functional index matching materials such as, for example, liquid crystal, pressure/temperature sensing materials, piezoelectric materials,
  • the present invention is directed to a wood-based light transmitting system, which comprises at least one transparent wood composite member formed from at least one wood block pre-cut from a natural wood in a predetermined angular relationship to a direction of natural internal channels in the natural wood and treated to remove lignin therefrom, thus forming lignin-devoid wood block, and
  • a filling polymer having refractive index substantially matching the refractive index of the cellulose-containing material of the natural internal channels' walls and substantially fully infiltrating the natural internal channels in the lignin-devoid wood block.
  • the transparent wood composite member has an upper and a bottom planes.
  • the predetermined angular relationship constitutes an angle, for example, of approximately 90° between the direction of the internal channels and at least one of the upper and bottom planes of the transparent wood composite member.
  • the upper and/or bottom planes are cut in a direction substantially coinciding with the direction of the natural internal channels in the transparent wood composite member.
  • Other angular relationship between 0° and 90° between the wood block's planes and the direction of the interval channels also is contemplated in the subject system and method.
  • the transparent wood composite member may be configured as a thick or thin block or a layer having a length of 1 mm or larger, a width of 1 mm or larger, and a thickness of 100 ⁇ m or larger.
  • the resulting transparent wood composite member has light transmittance, ranging approximately from 80% to 95%, and an optical haze ranging approximately from 80% to 100% in the visible light wavelength range from 400 nm to 1100 nm.
  • the optical properties depend, although not exclusively, on the choice of the infiltrating materials.
  • the subject wood-based light transmitting system may form an optoelectronic system with an advanced light management, including at least one of photonic systems, solar cells, photo-detectors, displays, and wide-angle lighting systems.
  • the transparent wood composite member When used in a solar cell which includes an optically active layer, the transparent wood composite member (shaped as a thin layer having a thickness ranging between 100 ⁇ m and 3 mm) is disposed in optical contact with the optically active layer. Light incident onto the transparent wood composite member is scattered along the light path therethrough prior to reaching the optically active layer in the solar cell.
  • the subject wood-based light transmitting system may be used as a light-harvesting building structure having a high mechanical strength with a fracture strength of 23.5-45 MPa and high ductility of the fabricated transparent wood composite member.
  • the mechanical properties depend, although not exclusively, on the choice of the infiltrating materials.
  • the present invention is directed to a method of fabrication of wood based light transmitting systems which comprises the steps of:
  • step (b) the subject fabrication process assumes:
  • preparing a lignin removal solution by mixing a solution of NaOH having a concentration of 2.5 mol/L in deionized water, and a solution of Na 2 SO 3 having a concentration of 0.4 mol/L in deionized water;
  • lignin removal chemicals include, but not limited to NaOH+Na 2 SO 4 (boil) (+H 2 O 2 ), NaClO, H 2 O 2 , NaClO 2 +Acetic Acid, NaOH (+H 2 O 2 ), NaOH+Na 2 S (+H 2 O 2 ), Na 2 S 2 O 4 +ZnS 2 O 4 , ClO 2 , CH 3 COOOH, H 2 SO 5 , CH 3 COOOH+H 2 SO 5 .
  • the subject fabrication process further includes:
  • the subject method further contemplates the steps of:
  • the subject method also contemplates the step of:
  • FIGS. 1A-1J illustrate schematically the manufacturing process of two types of wood blocks, where FIG. 1A depicts wood blocks pre-cut in cross-direction (R-wood) and longitudinal direction (L-wood); FIGS. 1B and 1C show the internal channels in R-wood and L-wood, respectively, FIGS. 1D and 1E show SEM images of the internal channels in R-wood and L-wood, respectively, FIG. 1F depicts schematically the lignin removal stage of the subject fabrication process, FIGS. 1G and 1H depicts the color change of the wood block during the lignin removal (Processes I) and bleaching routine (Process II) respectively, and FIGS. 1I and 1J are diagrams corresponding to lignin content vs. time in processes I and II, respectively;
  • FIGS. 2A-2E show schematically the subject process of fabrication of the cross-cut transparent wood composite, where FIG. 2A shows a natural wood, FIG. 2B shows a pre-cut slice of the natural wood, FIG. 2C shows (on a somewhat enlarged scale) a lignin-filled wood block cut out in the crossing direction relative to the internal channels from the wood block of FIG. 2B , FIG. 2D shows the wood slice of FIG. 2C , where lignin is removed, FIG. 2E shows the step of polymer infiltration, FIG. 2F shows the transparent wood block of FIG. 2D with the polymer infiltrating the natural inner channels of the wood, and FIG. 2G shows the transparent wood composite;
  • FIGS. 3A-3D show Scanned Electron Microscope (SEM) images, where FIG. 3A is an SEM image of the lignin-devoid wood block, FIG. 3B is a zoom-in lignin-devoid SEM image of FIG. 3A , FIG. 3C is an SEM image of the aligned cellulose nanofibers, and FIG. 3D is an SEM image of a polymer filled wood composite;
  • SEM Scanned Electron Microscope
  • FIGS. 4A-4L illustrate comparison between the transparent wood composite precut in cross direction (R-wood) to the inner channels and in longitudinal direction (L-wood) along the inner channel
  • FIGS. 4A and 4B show the transmittance measurements setups with two different anisotropic structures (cross and longitudinal directions) of the transparent wood
  • FIGS. 4C and 4D are photo images of the scattered light spot for R-wood and L-wood
  • FIGS. 4E and 4F are diagrams representative of the intensity distribution in X and Y directions in correspondence to FIGS. 4C and 4D , respectively
  • FIGS. 4G and 4H show the transparent R-wood sample placed directly on the grids and 5 mm above the grids, respectively
  • FIG. 4I and 4J show the L-wood sample placed directly on the grids and 5 mm above the grids, respectively
  • FIG. 4K is a diagram representative of the total transmittance for the natural R-wood, natural L-wood, transparent R-wood and transparent L-wood, respectively
  • FIG. 4L is a diagram representative of the optical haze of the R- and L-wood composites, respectively;
  • FIGS. 5A-5H are representative of comparison of structural characteristics of the R-wood and L-wood, where FIGS. 5A and 5B illustrate mechanical forces applied to transparent R-wood and transparent L-wood members, respectively,
  • FIG. 5C is a diagram representative of the experimental stress-strain curves for the natural R-wood and transparent R-wood samples, respectively
  • FIG. 5D is a diagram representative of the experimental stress-strain curves for natural L-wood and transparent L-wood samples, respectively
  • FIGS. 5E and 5F show SEM images of cross section of the natural R-wood and natural L-wood after the fracture of the stress-strain test, respectively
  • FIGS. 5G and 5H show the SEM image of the cross section of the transparent R-wood composite and transparent L-wood composite samples, respectively, after the fracture of the stress-strain test;
  • FIGS. 6A-6F show scanning electron microscope (SEM) images of the wood transformation during the fabrication process, where FIG. 6A is a cross section of the wood block showing open channels filled with lignin, FIG. 6B is an SEM image of the cross section of the wood slice where the lignin is removed (the resulting white wood is shown as an inset), FIG. 6C shows a cross section of the wood slice where the lignin is replaced by the refractive index matching polymer (the resulting transparent wood shown as an inset), FIG. 6D is a side view of the untreated R-wood highlighting the alignment of the internal microchannels, FIG. 6E is an SEM image showing the densely aligned CNF in the cell wall of the microfibers, and FIG. 6F is an SEM image showing the fibers of FIG. 6E , which have been randomly distributed after further processing to have a higher contrast showing the aligned fibers broken down into a randomly distributed network;
  • SEM scanning electron microscope
  • FIGS. 7A-7C show the comparison of transmittance between the fabricated transparent wood composite and natural wood, where FIG. 7A shows a non-transparent wood block, FIG. 7B shows a transparent wood composite member with a thickness of 1 mm, and FIG. 7C is a diagram representative of comparison of the total defused transmittance of the regional natural wood and the transparent wood composite;
  • FIG. 8A is a diagram representative of the transmittance characteristic of wood slabs with different percentage of lignin removed
  • FIGS. 8B and 8C are fluorescent images of the wood on different scale
  • FIGS. 8D-8G are fluorescent images of the wood with different weight percentage of lignin removal level
  • FIGS. 9A-9B demonstrate the haze characteristics of the transparent wood composite sample and its application to GaAs solar cell, where FIG. 9A shows the light scattering by the transparent wood composite, FIG. 9B is a diagram representative of the transmittance and haze, respectively, of the transparent wood composite sample used in the experiment, FIG. 9C is a schematic representation of distribution of the light incident on a solar cell using the wood transparent composite attached to the active layer, and FIG. 9D is a diagram representative of the current density vs. voltage characteristics for the bare GaAs cell and the GaAs cell with the light management transparent wood composite coating, respectively;
  • FIGS. 10A-10B show schematically an edifice with a transparent wood roof top ( FIG. 10A ) and a building material ( FIG. 10B ) made from the subject transparent wood composite which scatters the transmitted light in the forward direction to create substantially uniform lighting and is capable of reducing the conductive heat flow to maintain a substantially constant internal temperature;
  • FIG. 11A is a SEM image of the transparent wood microstructure
  • FIG. 11B is a top view of the guided light propagation in a thick transparent wood composite block
  • FIG. 11C is a diagram representative of a high transmittance and low reflectance with effective broadband forward scattering in the visible wavelength range through the 0.5 cm thick transparent wood window
  • FIG. 11D shows the transmitted beam pattern of a 45° laser beam incident on the transparent wood composite sample
  • FIG. 11E shows a diagram of the intensity of the light vs. the scattering angle in X and Y directions;
  • FIG. 12A is a diagram representative of the transmittance percentage vs. haze percentage of standard glass, transparent paper, and the subject transparent wood composite, respectively
  • FIG. 12B is a photographic evidence of the problematic glaring effect with glass in comparison with the uniform and comfortable lighting through the transparent wood composite
  • FIG. 12C is photographic evidence of the uniform light distribution inside the house model when using the subject transparent wood composite as daylight harvesting roof top in comparison with glass
  • FIG. 12D is a diagram representative of the light intensity distribution of the glass roof vs. the transparent wood composite roof;
  • FIG. 13A is an illustration of the radial and axial heat transport in the transparent wood composite
  • FIG. 13B is a diagram of the measured thermal conductivities of the standard glass, epoxy, axial and radial directions of the transparent wood, respectively;
  • FIG. 14A depicts an impact test of a piece of standard glass in comparison with the transparent wood composite of the similar thickness
  • FIG. 14B depicts diagrams of the strain-stress curves of the transparent wood composite and glass, respectively
  • FIG. 14C is photographic evidence that the transparent wood composite sample is water resistant and exhibits no obvious change after 72 hours immersion in water.
  • the transparent wood composites were fabricated by efficient and simple process including removing the light absorptive lignin to form the lignin-devoid wood block (in the first manufacturing stage best shown in FIGS. 1F and 2D ), and backfilling the nano/microsized channels in the lignin-devoid wood block with index-matching polymers (in the subsequent second manufacturing stage best shown in FIG. 2E ).
  • the refractive index (RI) mismatch can be greatly reduced and the light reflection can be suppressed to increase the wood sample transparency.
  • the well-defined internal channels in the natural wood have a low tortuosity, which permits rapid removal of the colored lignin deposited inside the internal channels. After lignin removal, the open internal channels allow fast infiltration by the polymer(s) to decrease the light scattering and increase the mechanical strength of the wood/polymer composite.
  • the resulting polymer infiltrated lignin-devoid wood block demonstrates optical transmittance of approximately 87 ⁇ 5% and a high optical haze of up to 80-100% over the broad spectrum in the visible wavelength range of 400 nm-1100 nm.
  • the subject process preserves the well-aligned microstructure of CNF in the natural wood upon the lignin removal and the polymer infiltration which contributes to effective incident light scattering.
  • the pre-cut wood block may have various thicknesses to form a thick block or a thin layer, for example, the thickness of the wood transparent composite block in the subject method may range from roughly 100 ⁇ m (typical paper thickness) to a millimeter, or thicker, for example, 1.4 cm.
  • the subject transparent wood composites have enhanced dimensional stability in water and humid environments depending on the filling material, which may be selected from a large group of index matching materials.
  • the structure When the thin layer of the subject transparent wood composite is attached to a GaAs solar cell as a light management coating, the structure demonstrates an enhanced efficiency of the solar cell by 18%.
  • the subject transparent wood composite also has been demonstrated as a valuable building material which is capable to efficiently harvest sunlight to provide consistent and uniform indoor lighting.
  • the vertically aligned transparent wood fibers in natural wood exhibit an efficient visible light guiding effect with a large forward to back scattering ratio.
  • the subject transparent wood effectively guides sunlight into the building.
  • Unique optical properties such as an extreme optical haze (>95%) in the broadband range and a high transmittance (>85%), lead to a uniform and comfortable indoor ambient lighting without a glare effect in buildings.
  • the transparent wood composite also has better thermal insulation than glass with at least three times lower thermal conductivity. Greenhouse gas emission from residential and commercial sectors can mainly be attributed to the energy use of buildings which is reduced by the use of the transparent wood.
  • the application of the subject energy efficient transparent wood building material can yield substantial energy savings with associated reductions in greenhouse gas emission.
  • the wood based transparent composites can find a range of potential applications in the next-generation energy efficient buildings.
  • the subject fabrication process begins with pre-cutting a wood block 10 from a natural wood 12 in a predetermined angular relationship to a direction of natural internal channels 14 extending along the trunk of the natural wood 12 .
  • the wood block 10 has two opposing planes, for example, upper and bottom cut planes 16 and 18 , respectively, which may be parallel or non-parallel each to the other.
  • the angular relationship between the cut planes 16 , 18 and the direction of the internal channels 14 may encompass any angular displacement between the direction of the internal channels 14 and the cut plane of the wood block 10 .
  • two angular relationships are presented in following paragraphs, including (1) cross sectional cut forming radial (R-wood) type of the wood block 10 , shown in FIGS. 1A-1B, 1D, 2C-2D, and 2F , and (2) longitudinal cut forming longitudinal (L-wood) wood block 10 as shown in FIGS. 1A, 1C, and 1E .
  • R radial
  • L-wood longitudinal cut forming longitudinal wood block 10
  • other angular relationships for cutting the wood block 10 ranging between R (90°) and longitudinal direction (0 or 180°) are also contemplated in the process of fabrication of the subject transparent wood composite structure.
  • the channels 14 in the wood are naturally filled with lignin 20 .
  • the channels 14 have walls 22 which are made from cellulose and/or hemicellulose.
  • the subject fabrication method contemplates the step of lignin removal, which is schematically shown in FIGS. 1F and 2D , where wood blocks are heated in water with chemicals NaOH and Na 2 So 3 in Process I, and bleached in solution of H 2 O 2 in water in Process II, both of which combinably constitute the lignin removal stage to form a lignin-devoid wood sample 24 .
  • the brown and yellowish wood block 10 gradually becomes lighter, and finally becomes white (white wood 24 ) due to the light scattering and the absence of light absorption by lignin.
  • the channels in the white wood block 24 are open to permit the subsequent infiltration of the lignin-devoid sample 24 with a refractive index-matching polymer to decrease the light scattering as shown in FIG. 2F-2G , thus forming a highly transparent wood composite 26 .
  • the subject process is applied to fabrication of R-wood, as well as L-wood, transparent composites, although with different process regimes due to the fact that in the R-wood type, the internal channels 14 are shorter and their openings 30 allow easier access by the chemicals (as shown in FIGS. 1B, 1D ) than in L-wood where the longer open channels 14 extend in the direction of planes 16 , 18 of the wood block 10 (as shown in FIGS. 1C and 1E ).
  • the processes of lignin removal and polymer infiltration are longer for the L-wood than for the R-wood.
  • the difference in the channels length in R-wood and L-wood dictates the difference in lignin-renewal and polymer-infiltration kinetics. Due to the fact that the channels lengths in the R-wood ( FIGS. 1B and 1D ) is much shorter than the lengths in L-wood ( FIGS. 1C and 1E ), the lignin removal and polymer infiltration faster in the R-wood slices.
  • FIG. 1A R-wood has open channels 14 perpendicular to the plane(s) 16 and 18 with a depth substantially the same as the thickness of the wood.
  • L-wood has the identical mesoporous open channels but the depth of the open channels corresponds to the length of the wood block 10 .
  • the difference in the anisotropic microstructure of R- and L-wood leads to a significant difference in lignin removal rate, where lignin can be extracted much easier in R-wood due to the open channels with a short depth ( FIGS. 1B and 1D ). It takes a longer time to extract lignin from L-wood ( FIGS. 1C and 1E ).
  • the open channels in wood are not uniform in diameter, ranging from 10 ⁇ m to 80 ⁇ m, which leads to the difficulty in removing lignin in L-wood.
  • wood blocks 10 with a dimension of 50 mm by 50 mm and a thickness of 3 mm were used.
  • pre-cut wood blocks 10 were soaked in boiling solution containing NaOH and Na 2 SO 3 (Process I) to dissolve part of the lignin content. Then the wood blocks were subsequently transferred into H 2 O 2 solution in water for bleaching, i.e., to remove the remaining lignin (Process II).
  • the lignin removing chemical is typically prepared as described in precious paragraphs.
  • lignin removal chemicals include, but not limited to NaOH+Na 2 SO 4 (boil) (+H 2 O 2 ), NaClO, H 2 O 2 , NaClO 2 +Acetic Acid, NaOH (+H 2 O 2 ), NaOH+Na 2 S (+H 2 O 2 ), Na 2 S 2 O 4 +ZnS 2 O 4 , ClO 2 , CH 3 COOOH, H 2 SO 5 , CH 3 COOOH+H 2 SO 5 .
  • FIGS. 1G and 1H The color comparison for lignin removal in R-wood and L-wood is shown in FIGS. 1G and 1H .
  • the color becomes lighter as lignin is being removed (identified by the duration of the process).
  • FIGS. 1G-1H the process for R-wood is much faster than that for L-wood evidenced by lighter samples of R-wood than the L-woods at the same process duration.
  • the experimental setup, shown in FIG. 1B can be scaled up to process a number of wood blocks at the same time for mass manufacturing.
  • FIGS. 1I and 1J The lignin removal was quantified in both types of woods ( FIGS. 1I and 1J ), where the y-axis corresponds to the lignin content of the wood blocks after a certain period of time for the lignin removal processes I and II.
  • the lignin was removed rapidly in the first hour, where the lignin loss for R-wood is higher, up to ⁇ 25%.
  • FIG. 1I shows clear differences in lignin removal kinetics, where the process is much faster in R-wood than in L-wood.
  • the lignin in R-wood is also removed rapidly ( FIG. 1J ).
  • FIG. 3A shows the SEM image of a wood block after most of lignin has been removed.
  • the open channels are made of cellulose and hemicellulose.
  • the wood block displays massive open channels and openings along the wood growth direction.
  • Zoomed-in SEM shown in FIG. 3B ) also shows the smaller, secondary holes which enables material transport in the radial directions in the wood trunk.
  • the inset of FIG. 3B shows the lignin-devoid white wood block 24 .
  • zoom-in SEM image also shows the cellulose nanofibers on the cell walls 22 , which are aligned and densely packed as shown in FIG. 3C .
  • the filling polymer 28 may be a material from a group of material having a refractive index close to the refractive index of cellulose ( ⁇ 1.48).
  • the filling polymer may be selected from, but not limited to, the group of materials, including:
  • Thermosetting polymers such as, for example, Polyester fiberglass, Polyurethanes polymers, Vulcanized rubber, Bakelite, Duroplast, Urea-formaldehyde, Melamine resin, Diallyl-phthalate (DAP), Polyimides and Bismaleimides, Cyanate esters or polycyanurates, Furan resins, Polyester resins, Silicone resins, Benzoxazine resins, Bis-Maleimides (BMI), Cyanate ester resins, Epoxy (Epoxide) resins, Phenolic (PF) resins, Polyester resins, Polyimides, Polyurethane (PUR) resins, Silicone Resins, Vinyl ester resins,
  • Polyester fiberglass Polyurethanes polymers
  • Vulcanized rubber Bakelite, Duroplast, Urea-formaldehyde
  • Melamine resin Diallyl-phthalate (DAP)
  • DAP Diallyl-phthalate
  • Polyimides and Bismaleimides Cyanate esters or polycyanur
  • Thermoplastic polymers such as, for example, Acrylic, ABS, Nylon, PLA, Polybenzimidazole, Polycarbonate, Polyether sulfone, Polyetherether ketone, Polyetherimide, Polyethylene, Polyphenylene oxide, Polyphenylene sulfide, Polypropylene, Polystyrene, Polyvinyl chloride, Teflon,
  • Cellulose derivatives such as, for example, Cellulose acetate, Cellulose acetate butyrate, Cellulose triacetate, Methyl cellulose, Hydroxypropyl methyl cellulose, Ethyl cellulose, Hydroxyethyl cellulose, Carboxymethyl cellulose, Dissolved cellulose, Nanofibrillated cellulose, Cellulose nanocrystals,
  • functional index matching materials such as, for example, liquid crystal, pressure/temperature sensing materials, piezoelectric materials,
  • transparent liquid epoxy resin precursor with low viscosity
  • transparent liquid epoxy resin precursor with low viscosity
  • a mixture of a resin and non-blushing cycloaliphatic hardener polyvinylpyrrolidone (PVP), Poly(methyl methacrylate) (PMMA), Poly(vinyl alcohol) (PVA), Polydimethylsiloxane (PDMS), etc.
  • PVP polyvinylpyrrolidone
  • PMMA Poly(methyl methacrylate)
  • PVA Poly(vinyl alcohol)
  • PDMS Polydimethylsiloxane
  • the lignin-devoid white wood sample 24 is immersed in the liquid polymer 28 followed by repeated cycles of vacuum/de-vacuum processing, as schematically shown in FIG. 2E .
  • a complete infiltration is achieved after about three vacuum/de-vacuum cycles.
  • SEM image in FIG. 3D and schematics in FIG. 2F show that the filling polymer fully infiltrates the channels and apertures.
  • the original cellulose walls of wood channels and the infiltrating polymer can be clearly distinguished in the SEM image in FIG. 3D .
  • Full infiltration was confirmed in the experiments by breaking the wood-polymer composite in the middle followed by the SEM imaging.
  • the polymer infiltration process does not destroy the frameworks of the natural wood microstructures.
  • FIGS. 4A-4L illustrate the optical measurement for the two types (R-wood and L-wood) of transparent wood composites 26 , respectively.
  • the thickness of both R-wood and L-wood for the study was 2 millimeter for comparison purpose.
  • FIGS. 4A and 4B The transmittance measurement setups for transparent R-wood and transparent L-wood composite samples 26 are shown in FIGS. 4A and 4B , respectively.
  • a 532 nm single mode laser (from Thorlabs, Inc) was used as the incoming light source for the anisotropy measurements. The laser was collimated first with a spot size around 200 ⁇ m before perpendicularly illuminating the transparent wood samples. The incoming light rapidly diverges due to the scattering in transparent wood composites. While the scattering effect is isotropic in the light propagation cross-section plane for R-wood (as shown in FIG. 4C ), the light scattering in L-wood is highly anisotropic (as shown in FIG. 4D ).
  • a photodiode power sensor S130C from Thorlabs, Inc. was used to record the scattered light intensity distribution in both the x and y direction in R-type and L-type (marked in FIGS. 4E and 4F , respectively) of the 2-dimensional plane perpendicular to the light propagation direction (z direction).
  • the index mismatch between the filling polymer and the cellulose fibers facilitates angle-independent scattering of the single mode Gaussian laser beam, as shown in FIG. 4E .
  • the resulting scattered light thus exhibits a Gaussian-like distribution with similar scattering angle in both the x and y directions.
  • the wood fibers in the L-wood are aligned in the x direction, yielding a discrete index variation in y direction (as shown in FIG. 4F ).
  • a greatly traversely-expanded beam is observed in the y direction with an extremely large scattering angle, which resulted from a strong light diffraction by densely packed and aligned wood fibers.
  • In the x direction there is little refractive index fluctuation, and the incident light is scattered slightly, which resulted in a mild light space distribution.
  • the strong anisotropic microstructures in L-wood lead to its intense anisotropic optical properties.
  • the anisotropic transparent wood composites also exhibit unique imaging effects.
  • a grid 32 with perpendicular and parallel lines was designed to show the angle dependence in light scattering (as shown in FIGS. 4G-4J ).
  • the grid lines can be clearly seen for both the transparent R- and L-wood transparent composite samples 26 when in contact with the surface of grid lines ( FIGS. 4G and 4I ).
  • the visual effect is different when the transparent wood composites 26 positioned 5 millimeters above the lines.
  • the grid lines are turned to parallel lines, while the lines parallel to the open channels diminish, which is in accordance with the anisotropic haze effect shown in FIG. 4F .
  • FIGS. 4K and 4L In addition to the anisotropic behavior of optical properties, the total transmittance and optical transmittance haze of the transparent wood composite has also been studied ( FIGS. 4K and 4L ).
  • An integrated sphere was used to measure the optical transmittance and transmittance haze.
  • Natural L- and R-wood show almost negligible transmittance due to the strong lignin absorption.
  • both types of transparent wood composites show dramatically high transmittance as illustrated in FIG. 4K .
  • the measured R-wood transmittance reaches up to 90%, higher than in the L-wood, which is due to better filling of the polymer due to the small depth for the open channels in R-wood.
  • Both transparent wood composite samples exhibit large haze covering the entire visible wavelength ranging from 400 nm to 800 nm, while R-wood shows a generally higher value than that of L-wood ( FIG. 4L ).
  • the scattering intensity is substantially independent of the wavelength.
  • This broad range light management is referred to as Mie scattering.
  • the high optical haze as exhibited by both types of wood can be potentially used for a wide range of optoelectronics applications where advanced light management is needed to improve the light coupling and extraction efficiency needed in solar cells and displays.
  • transparent wood samples 26 and transparent L-wood samples 26 were fabricated having a shape shown in FIGS. 5A-5B , respectively, with dimensions of about 50 millimeters long, 10 millimeters wide and 3 millimeters thick for mechanical tests.
  • the samples 26 are shown in FIGS. 5A-5B with channels 14 extending in crossing and longitudinal directions, respectively, between the cut planes 16 , 18 .
  • a Tinius Olsen H5KT tester was used to carry out the stress-strain measurement for the samples. Natural wood samples cut into similar dimensions were also evaluated for comparison.
  • the transparent wood composite shows an improved mechanical strength, with a fracture strength up to 23.5 MPa (as presented on the diagram in FIG. 5C ).
  • the fracture strength of the natural R-wood is only 4.5 MPa. Lignin removal and polymer filling lead to the transparent R-wood material with improved strength ( FIG. 5C ).
  • An additional benefit is that the transparent wood composite possesses a ductility similar to the nature wood, i.e., ⁇ 3.7%.
  • the transparent L-wood has a fracture strength of about 45 MPa, around 2 times higher than that of transparent R-wood (as presented in the diagram in FIG. 5D ).
  • Transparent L-wood also has a higher ductility than the transparent R-wood. Compared with the natural L-wood, the transparent L-wood after polymer infiltration has a higher both strength and ductility.
  • the cross section after the stress-strain test until fracture occurred has been studied by the inventors.
  • the open channels in the natural wood are visible in the SEM images, shown in FIGS. 5E and 5F .
  • the force applied is perpendicular relative the open channels in the R-wood, and is parallel to the channels in the L-wood.
  • FIGS. 5G and 5H show cross section SEM of the transparent R-wood and transparent L-wood, respectively, after fracture in the stress-strain test.
  • the inset in FIGS. 5E-5H is the photo of the samples after mechanical fracture.
  • anisotropic wood composites Two types have been manufactured by taking advantage of the unique natural macrostructures in natural wood. In both transparent R-wood and L-wood composites, two stages in sequence were used to fabricate anisotropic transparent wood composites: (1) lignin removal from the open channels, and (2) polymer infiltration into the open channels. The well-defined, aligned channels largely facilitate the two processes. In both types of the transparent wood, the nature cellulose structures are well preserved, the colour of lignin is removed, and the porous structure is filled with a polymer, which leads to a high transmittance of up to 90%.
  • the numerous polymer-cellulose interfaces support the forward light scattering, which leads to a high optical haze at the same time.
  • the two types of transparent wood composites (R-wood and L-wood) also display different light scattering and mechanical properties.
  • the transparent wood with open channels in the plane (L-wood) is mechanically stronger and tougher than the plane (R-wood).
  • the chemicals used in removing lignin contents from wood were sodium hydroxide (>98%, Sigma-Aldrich), sodium sulphite (>98%, Sigma-Aldrich) and hydrogen peroxide (30% solution, EMD Millipore Corporation).
  • the polymer used for infiltration was Epoxy Resin (#300 resin and #21 non blushing cycloaliphatic hardener, AeroMarine Products, Inc.).
  • Polyvinylpyrrolidone (PVP, average M w ⁇ 1,300,000, Sigma-Aldrich) was used as the filling polymer in the lignin-devoid wood.
  • the solvents used were ethanol alcohol (190 proof, 95%, Pharmco-Aaper) and deionized (DI) water.
  • the lignin removal solution was prepared by dissolving NaOH and Na 2 SO 3 in deionized (DI) water resulting in a concentration of 2.5 mol/L and 0.4 mol/L, respectively.
  • the wood slices were immersed in the lignin removal solution and boiled for 12 hours, as shown in FIG. 1F (Process I), followed by rinsing in hot distilled water three times to remove most of the chemicals.
  • the wood blocks were subsequently placed in the bleaching solution (H 2 O 2 , 2.5 mol/L in DI water) and boiled without stirring (Process II shown in FIG. 1F ). When the yellow color of the samples disappeared, the samples were removed and rinsed with cold water.
  • the lignin-devoid samples were then preserved in ethanol
  • Epoxy Resin was prepared by mixing the two liquid components (#300 resin and #21 non blushing cycloaliphatic hardener) at a ratio of 2 to 1.
  • the lignin-devoid wood samples were placed at the bottom of a dish and immersed in the liquid resin.
  • the solution was then degassed (vacuum) under 200 Pa to remove the gas and ethanol solvent in wood as shown in FIG. 2E .
  • the vacuum was released to allow the polymer filling into the wood structure at atmosphere pressure.
  • the process vacuum/de-vacuum was repeated for 3 times as shown in FIG. 2E . All these processes were terminated within 30 minutes to avoid the polymer solidification.
  • the dish containing the wood sample and polymer was kept static (undisturbed) at 30° C. for 12 hours.
  • the polymer-infiltrated wood sample was peeled from the dish after the polymer was completely solidified.
  • the polymer When using Polyvinylpyrrolidone (PVP), the polymer was dissolved in ethanol at a concentration of 15% by mass of polymer. After full dissolution, the lignin-devoid wood was placed at the bottom of a dish and immersed in a PVP solution. The solution depth was approximately an order of magnitude greater than the wood thickness. The solution was then degased under 200 Pa for approximately 10 minutes to ensure full infiltration. Finally, the dish was placed on a hot plate at 60° C. The polymer-infiltrated wood sample was peeled from the bottom of the dish after the solvent was completely evaporated.
  • PVP Polyvinylpyrrolidone
  • the morphologies of the transparent wood composite were characterized by a scanning electron microscope (SEM, Hitachi SU-70). The transmittance spectrum and haze were measured with a UV-Vis Spectrometer Lambda 35 (PerkInElmer, USA.). The lignin contents were measured by the standard methods for lignin determination (Technical Association of Pulp and Paper Industry Standard Method T 222-om-83).
  • Photocurrent-voltage characteristics of solar cells were monitored with a voltage-current source meter (2400 Keithley) illuminated by an Orel Solar Simulator (AM 1.5, 100 mW/cm ⁇ 2 ) with a scan rate of 10 mV/s.
  • a 532 nm single mode laser DJ532-10 (Thorlabs Inc.) was used as the incoming light source with stabilized output power.
  • the laser was collimated first with a spot size around 200 ⁇ m before perpendicularly illuminating the samples.
  • the Gaussian beam quickly diverges after propagating through the transparent wood composite.
  • a photodiode power sensor S130C from Thorlabs was used to record the scattered light distribution in the 2-dimensional plane perpendicular to the light propagation direction.
  • a pinhole with a constant diameter of 5 mm was placed in front of the photo diode to record the light power at various angles along x and y directions.
  • the mechanical properties were structured using a Tinius Olsen HSKT testing machine. The wood was selected without joints or fasteners with a dimension of about 50 mm ⁇ 10 mm ⁇ 3 mm
  • Anisotropic channels are found within the trunks of most trees. These mesoporous channels have a diameter of 25 ⁇ m to 50 ⁇ m and allow the extraction of lignin along the channel direction. Dry basswood slabs of typical thickness in the range of 100 ⁇ m to 14 mm were obtained by cutting perpendicular to the tree growth direction. The open channels in the thin sections enable the fast removal of lignin from the wood slab.
  • basswood contains 18% to 21% lignin and 79% to 82% hemicellulose and cellulose by mass.
  • the SEM image of the sample 10 before lignin 20 removal is shown in FIG. 6A .
  • Lignin 20 was extracted from the channels 14 and apertures 30 by the chemical processes of NaOH treatment followed by H 2 O 2 bleaching.
  • the wood slab 10 gradually lost its color (as the lignin was being removed), and became visibly whiter due to the large light reflection at the interfaces.
  • the brown color of the natural wood diminished gradually and finally changed to snow white (the inset 24 shown in FIG. 6B ).
  • FIGS. 6B and 6D By controlling the speed and duration of the lignin removal process, the lignin was removed almost entirely while simultaneously preserving the microstructure of the wood, as shown in FIGS. 6B and 6D . It is noteworthy that well-aligned microstructure in the wood block was successfully preserved after the lignin removal process ( FIGS. 6E and 6F ).
  • Index-matching polymers 28 were used to fill the lignin-devoid channels 14 and to reduce light scattering to attain high optical transmittance.
  • Polyvinylpyrrolidone (PVP) 28 was selected (from a number of different refractive index matching polymers) as the filling material because of its excellent transparency, relatively low viscosity in ethanol and good wettability on cellulose. These characteristics of PVP enabled it to fully permeate the micro-scale apertures 30 in wood. PVP is environmentally friendly and biodegradable, similar to wood nanofibers.
  • FIG. 6C shows a scanning electron microscope (SEM) image of the wood block after PVP polymer filling, where all the apertures 30 and channels 14 between the cellulose walls have been completely filled with polymer 28 .
  • SEM scanning electron microscope
  • the polymer infiltration into the wood microstructures also mechanically glues the wood cellulose nanofibers (CNF) together.
  • the subject method for fabricating transparent wood composites allows the original alignment of CNF to be preserved.
  • FIG. 6D illustrates the cell walls of the channels 14 and apertures 30 .
  • the CNF are clearly aligned without being affected (as shown in FIG. 6E ). These aligned CNF lead to enhanced mechanical properties. The close packing of the aligned CNF complicates their characterization by SEM. The snow-white wood 24 has been further disintegrated for a longer period of time to achieve satisfactory SEM with a higher contrast. Upon further processing, the aligned fibers were broken down into a randomly distributed network as is depicted in FIG. 6F .
  • the optical properties can be more finely tuned with polymers of different refractive indexes.
  • FIG. 7A shows a natural wood block 10 measuring 30 mm ⁇ 22 mm ⁇ 1 mm.
  • the wood composite 26 shown in FIG. 7B is highly transparent and the text underneath is clearly visible.
  • the diagram of measured transmittances of the transparent wood and the original wood are shown in FIG. 7C .
  • the natural wood 10 in FIG. 7A shows zero transmittance at wavelengths from 400 nm to 600 nm, which is mainly due to the large light absorption of the lignin matrix. The maximum transmittance does not exceed 25% over the measured range of wavelengths.
  • the transparent wood 26 FIG. 7B
  • FIG. 8A shows the transmittance of wood with different amounts of lignin. Overall, the absorption edges shift to longer wavelengths with increasing lignin content.
  • curve A untreated
  • line B lignin removal
  • LR lignin removal
  • lignin exhibits fluorescence emission since it contains chromophores.
  • Photoluminescence techniques were used to verify the lignin content in the wood samples with varying amounts of lignin. Fluorescence images of wood with different weight percentage of lignin removal (LR) level are shown in FIGS. 8D-8G , beginning from wood sample 10 (in FIG. 8D ) to lignin-devoid wood sample 24 (in FIG. 8G ). In general, they are in agreement with the results presented in the TAPPI standard lignin measurement method which uses luminescence to reveal the presence of lignin. It is seen that the fluorescence intensity for original wood is weaker than the 33% LR sample.
  • the transparent wood composites exhibit high transmittance haze.
  • Light scattering by the transparent wood composite is shown in FIG. 9A .
  • the measured haze is around 80 ⁇ 5% over the wavelength range from 400 nm to 1100 nm. This is a very unique property compared to transparent glass or plastic materials with haze less than 1%.
  • the transparent wood composite haze is also much higher than that of the ultrahigh haze nanopaper, which exhibits a haze value of approximately 60%.
  • the high haze in transparent wood composites originates from the unique microstructure of wood.
  • cellulose microchannels are the predominant structural component of wood. Each microchannel is composed of microfiber units that can be further processed into nanofibers. There are two reasons for the measured high haze. First, the wood fibers and channels often have micro-curvatures with bumps, microstripes and microcavities ( FIG. 6D ), causing them to function as light reflection/scattering centers. Second, the microfibers and microchannels can guide the incident light along the axial direction for efficient forward scattering.
  • transparent wood composites were demonstrated when used as a substrate for a GaAs solar cell 40 shown in FIG. 9C .
  • light management plays an important role.
  • the subject transparent wood composites, with their high transmittance and high haze serve as efficient light management coatings or substrates for optoelectronic devices, such as photodetectors and solar cells.
  • the transparent wood 26 used for the solar cell 40 had a transmittance of around 90% and a haze of about 80% over a broad wavelength range.
  • a drop of ethanol was deposited on the surface of the existing solar cell 40 .
  • the transparent wood was placed on top of the cell to form contiguous contact with the active layer 42 .
  • the sandwich structure was allowed to dry at room temperature until the wood was firmly attached to the surface of the bare GaAs solar cell.
  • the measured current density-voltage (J-V) characteristics of the solar cell are shown in FIG. 9D .
  • the solar cell's electronic properties, including short circuit density (J SC ), open circuit voltage (V OC ), fill factor (FF, the ratio of the maximum output power solar the product of V OC and J SC ) and the overall conversion efficiency, which are extracted from the J-V curves, are presented in Table I which reflects the comparison of electrical properties of GaAs solar cell before and after the attachment of a transparent wood composite substrate.
  • the Jsc enhancement is 10.1 ⁇ 3%, less than that of the transparent wood coating.
  • a slight enhancement in fill factor has also been observed, which serves as an indicator that the dark saturation current has not been degraded.
  • the transparent wood substrate significantly improves the performance of a bare GaAs solar cell as a light management layer, similar to the effects observed with transparent paper.
  • the high transmittance allows light to reach the surface of GaAs solar cell with less loss. The normal incident light becomes diffusive when it reaches the solar cell's top surface due to the high haze.
  • This phenomenon results in increasing the travelling path of photons in the solar cell and improves the possibility of a photon being captured within the cell's active region. Additionally, the decreased refractive index mismatch between GaAs and air after wood coverage allows light reflection to be suppressed leading to an increased light flux into the solar cell.
  • the application of the transparent wood has also been demonstrated as an energy efficient light harvesting building material with the following advantages.
  • First, the subject transparent wood can efficiently harvest sunlight with a broadband transmittance of >85%. Due to the extremely high haze ( ⁇ 95%) of transparent wood, the indoor illumination can be maintained substantially uniform and consistent.
  • Second, the transparent wood exhibits a directional forward scattering effect, which can be used to effectively guide sunlight into the building.
  • the thermal conductivity along and across the wood channels was measured to be as low as 0.32 and 0.15 W m ⁇ 1 K ⁇ 1 , respectively.
  • the wood composite When used as a transparent building material, the wood composite can provide improved thermal insulation with respect to standard glass and in reducing air conditioning usage.
  • FIG. 10A illustrates the usage of transparent wood 26 as a sunlight harvesting rooftop.
  • FIG. 10B the transmitted light intensity distribution is insensitive to the direction of the sun, keeping the indoor light consistent throughout the day.
  • the conductive heat flow can also be reduced with a more consistent indoor temperature.
  • the transparent wood used as a window or rooftop material would pay for itself by providing cost savings in lighting and air conditioning energy indoors usage.
  • FIG. 11A is a scanning electron microscopy (SEM) image of a basswood block where the wood cells (channels) are naturally aligned along the direction of growth.
  • infiltration polymers There are many suitable choices for infiltration polymers as long as the refractive index is close to 1.5 and the material has a low viscosity. With the small refractive index mismatch between the cellulose and the epoxy, light can propagate along the growth direction while the wood cells (channels) function as lossy waveguides with a diameter ranging from tens to hundreds of micrometers depending on the species of natural wood.
  • the DJ532-10 (Thorlabs, Inc.), 532 nm green single mode laser was used as the incoming light source with a spot size of 200 ⁇ m.
  • the beam is incident from the right hand side with a 45° input angle and is indicated by the arrow in FIG. 11A .
  • a wood block with a large thickness of 1.4 cm was used so that the propagation of the beam inside the wood block can be clearly observed.
  • the beam quickly diverges after reaching the top surface of the wood and then propagates along the wood channel direction.
  • the bright laser light is well directed, indicating an efficient guiding effect.
  • the light confinement inside the wood is mainly determined by the wood channel alignment direction instead of the incident light angle.
  • the densely packed and vertically aligned channels of the transparent wood 26 function as cylindrical broadband waveguides with high propagation scattering losses.
  • This unique light management capability of the transparent wood cells results in a macroscopic light propagation effect with a large haziness.
  • the optical properties including haze, forward transmittance, and backward reflection are summarized in FIG. 11C .
  • the results show that the transparent wood exhibits a high transmittance around 90% and a simultaneously high optical haze around 95%. By taking an averaging 90% transmittance and ⁇ 10% reflection within the wavelength range from 500 to 1100 nm, a directional forward to back scattering ratio as high as 9 was obtained.
  • nanostructures including nanocones and nanospheres are often used in order to achieve directional scattering under the light management schemes using Mie scattering.
  • the spectral response is usually sensitive to wavelength and the forward to back scattering ratio is often less than that exhibited by transparent wood cells. While exhibiting a high transmittance, the haze of the transparent wood can exceed 95% which is likely due to the scattering of the vertically propagating light by microstructural roughness.
  • the overall transparency for the transparent wood composite is comparable to standard glass, plastic, and cellulose-based nanopaper confirming the effectiveness of the herein developed procedure for transparent wood composites.
  • FIG. 11D shows a schematic of the single mode laser at a tilted angle incident on a transparent wood sample 26 with the transmitted light pattern captured on the screen.
  • the beam intensity does not show notable deviation from a standard Gaussian distribution.
  • Light management plays a crucial role in the effort to improve the overall conversion efficiency of solar cells and light emitting diodes (LEDs).
  • the subject transparent wood composites with their unique light management capability, can serve as an effective transparent coating or substrate materials for building integrated photovoltaic.
  • FIG. 12A is representative of comparison studies of the haziness of transparent wood, haze paper, and glass.
  • the haze of the transparent wood composite reaches 95% and is much higher than that of the ultrahigh haze nanopaper, which exhibits a typical haze value of ⁇ 60%.
  • a wooden house model FIG. 12C was built with a transparent wood roof 8 cm ⁇ 12 cm.
  • Sources of glare include the morning and evening positions of the sun, ice, reflective surfaces on cars, highly polished floors, and the windows of nearby buildings. Glare can interfere with the clarity of a visual image.
  • the transparent wood is shown to provide an effective antiglaring effect.
  • glare is completely removed while a more uniform brightness is obtained as demonstrated in FIG. 12B .
  • FIG. 12C the effectiveness of using soda-lime glass and transparent wood, respectively, is compared as a light harvesting roof
  • a solar simulator from Oriel Instruments-Newport was used as the white light source.
  • Oriel Instruments-Newport was used as the white light source.
  • uniform indoor illumination was observed.
  • the high haze and high transparency of the wood composite resulted in maximized sunlight harvesting and a much consistent light distribution over the course of a day.
  • a calibrated Si detector from Thorlabs was used to evaluate the light distribution inside the house model. Six different spots were selected and marked as 1-6 for the glass top house and the transparent wood top house, respectively. The results are shown in FIG. 12D .
  • the maximum light intensity inside the glass roof house is 12.3 mW cm ⁇ 2 while the minimum light intensity is only 0.35 mW cm ⁇ 2 , making the illumination non-uniformity greater than 35.
  • the light intensity difference between brightest corner (4.9 mW cm ⁇ 2 ) over the darkest corner (2.1 mW cm ⁇ 2 ) is 2.3.
  • the transparent wood building material has been experimentally shown to be an effective solution to save indoor lighting energy and to provide uniform illumination with enhanced visual comfort and privacy protection due to its intrinsic haziness.
  • the transparent wood composites provide a high resistance to phonon traveling in the wood fiber microstructure.
  • the radial heat travelling pathway yields an even larger phonon scattering effect than that in the axial direction.
  • the anisotropic thermal properties of the transparent wood can be attributed to the alignment of wood cells, which has been well-preserved after lignin removal and polymer infiltration.
  • a thermal conductivity of around 0.32 W m ⁇ 1 K ⁇ 1 was measured in the axial direction and 0.15 W m ⁇ 1 K ⁇ 1 in the radial direction, comparable to the thermal conductivity of original basswood.
  • a bulk polymer block (the same polymer that has been infiltrated into wood) shows a higher thermal conductivity of around 0.53 W m ⁇ 1 K ⁇ 1 .
  • the resulting lower thermal conductivity of transparent wood is due to the high phonon resistance across the wood cell walls (mainly cellulose and hemicellulose) and the multiple interfaces phonon scattering effect.
  • the mechanical properties can further be tuned by the choice of the infiltrating materials.
  • glass Fisher Scientific Microscopic Glass
  • Glass has presented significant safety concerns when used as a building block for residential and commercial structures. When glass undergoes a sudden impact such as flying debris, an earthquake, or even sudden movement of the occupants, glass can break and spray shattered pieces. Sometimes, glass can have sudden and spontaneous failure caused by edge or surface damage which propagates through creep loads. The breaking of glass requires immediate maintenance and attention, since the shattered glass presents severe safety issues. On the other hand, wood can withstand higher impact owning to the Van der Waals interactions between the cellulose and the energy absorbing polymer infiltrated microstructure.
  • FIG. 14A shows the resulting morphology of glass and transparent wood 26 after fracture due to a sudden hit from a dropping sharp object.
  • the glass shattered immediately into pointed pieces while the shock-resistant transparent wood stays intact.
  • Glass is fairly rigid, but can be brittle as well. When glass is under a load it can only accommodate stress to a relatively low level and then suddenly fail. Once a crack starts in glass, there is little within its structure to stop it from propagating. Consequently, glass exhibits a linear curve in strain and stress curve as shown in FIG. 14B .
  • the subject transparent wood composite possesses a much higher strain of 6%, more than two orders higher than that of standard soda-lime glass. This substantial increase in ductility is highly desirable for the application as a structural material. Even after breaking upon a sudden impact, the transparent wood is only bent and split instead of shattering into multiple sharp pieces. For commercial application as a building material, the transparent wood is also required to be water-resistant.
  • the transparent wood sample 26 was immersed in water as shown in FIG. 14C . After 72 hours, the sample was intact without any shape distortion or any degradation in mechanical and optical properties.
  • the SEM observation of the epoxy filled wood walls and the mechanical properties of the transparent wood after 72 hours of water immersion have additionally been studied. The results show that water has negligible effect on the properties of the transparent wood potentially due to the encapsulation of the polymer component.

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