Determination of the Adhesive Content of Medium Density Particleboards Produced with Bio-based Polymer

This work contributes to the use of alternative adhesives in the wood-based industry,where pine wood is commonly used.The investigation identifies the influence and the optimal content(8,12 and 15wt%)of a bio-based polyurethane adhesive in the production of medium density particleboards(MDP).A compaction pressure of 4 MPa at 100oC for 10 minutes is considered in the manufacture of panels based on pine wood residues and bio-based resin.The bulk density,flexural modulus(MOE)and strength(MOR)properties under static three-point bending are obtained according to the Brazilian standard NBR 14810.The results are compared with NBR 14810 and other standards to verify its performance based on the minimum requirements.Bulk density is not significantly affected by the investigated adhesive levels.MOE and MOR reach average values equivalent to 12wt%and 15wt%of the adhesive,and both meet the minimum requirements established in international normative documents.The adhesive level range responsible for maximizingρ,MOE and MOR is between 12.42wt%and 15.79wt%.

Synthetic Process of Bio-Based Phenol Formaldehyde Adhesive Derived from Demethylated Wheat Straw Alkali Lignin and Its Curing Behavior

Lignin is a natural biopolymer with a complex three-dimensional network, commercially obtained from wasteliquid of paper pulp and bioethanol production, and could be a candidate for preparation of environment-friendlybio-based polyphenol material. In the present work, the demethylated wheat straw alkali lignin (D-Lig), preparedby demethylation of wheat straw alkali lignin (Lig) using an in-situ generated Lewis acid, was used to synthesizebio-based phenol formaldehyde resin adhesive (D-LPF) applied in plywood. Effects of synthetic process’s factors,including lignin substitution for phenol, NaOH concentration and molar ratio of formaldehyde to phenol, on thebonding strength and free formaldehyde content of D-LPF were investigated in detail, and the optimum syntheticprocess of D-LPF was obtained as following: Lignin substitution for phenol 60%, NaOH concentration 5.0% andmolar ratio of formaldehyde to phenol 2.0, and under the optimum reaction condition, the D-LPF presented lower free formaldehyde content (0.18%) and higher bonding strength (2.19 MPa), which was better than those ofcontaining-lignin phenol formaldehyde resin adhesive (LPF). Additionally, the curing behavior of the adhesivewas studied by differential scanning calorimetry (DSC) combined with gel time. It can be obtained that D-LPFresin adhesive had the shortest gel time, and fastest curing rate, compared with those of PF and L-PF resin adhesives. The curing kinetics data was fitted well by Kissinger model using non-isothermal DSC method, and theaverage activation energy value was 85.3 kJ/mol, slightly higher than that of commercial PF resin, while lowerthan that of LPF (90.2 kJ/mol). Finally, based on the analytical results of high temperature fourier transform infrared spectroscopy (FTIR), a possible curing mechanism of D-LPF was proposed.

Xanthan Gum—Bio-Based Raw Material for Wood Adhesive

Due to their lower environmental impact, ease of accessibility, low cost, and biodegradability, bio-renewable sources have been used extensively in the last several decades to synthesize adhesives, substituting petrochemical-based adhesive. Vegetable oils (including palm, castor, jatropha, and soybean oils), lactic acid, potato starch, and other bio-renewable sources are all excellent sources for the synthesis of adhesives that are being taken into consideration for the synthesis of “eco-friendly” adhesives. Due to their widespread use, accessibility, affordability, and biodegradability, biobased raw materials like carbohydrates used to synthesize wood and wood composite adhesive have gradually replaced petrochemical-based adhesive. Recently, xanthan gum, a naturally occurring polymer, has drawn the interest of scientists as a potentially petroleum source replacement. It possesses specific rheological characteristics, excellent water solubility, and stability to heat, and can be used as a binder, thickener, suspending agent, and stabilizer. Xanthan gum increases the adhesive strength in addition to increasing the viscosity of water-soluble adhesives. This article discusses xanthan gum as a potential substitute for traditional raw materials derived from petroleum that is used as a raw material for adhesives.

Overview of the Synthesis, Characterization, and Application of Tannin-Glyoxal Adhesive for Wood-Based Composites

More than a century after its initial synthesis,urea-formaldehyde(UF)resins still have dominant applications as adhesives,paints,and coatings.However,formaldehyde in this industry produces formaldehyde emissions that are dangerous to health.Scientists have spent the last decade replacing formaldehyde and phenol with environmentally friendly substances such as glyoxal and tannin to create bio-based adhesives.This review covers recent advances in synthesizing glyoxal tannin-based resins,especially those made from sustainable raw material substitutes and changes made to synthetic processes to improve mechanical properties.The efficacy of using tannin-glyoxal adhesives in producing wood-based composites has been proven.The glyoxylate reaction forms cross-linked bridges between the aromatic sites of the tannin and glyoxal molecular structures.Glyoxal tannin adhesive with a greater percentage of glyoxal than tannin will produce an adhesive with better characteristics.The gel time reduces as the hardener concentration rises from 7.5%to 15%when glyoxal is used in adhesives.However,excessive amounts of glyoxal will result in a decrease in viscosity values.Glyoxal exhibits faster delivery degradation when it reaches a maximum temperature of approximately 130°C,although it initiates the curing process slightly slower at 110°C.Adding glyoxal to tannin-based adhesives can improve the mechanical properties of composite boards.The wet shear strength of the resulting plywood is increased by 105.4%with the addition of 5-weight percent tannin-based resin with glyoxal as a cross-linker in Soy Protein Adhesive.With glyoxal as a hardener,the panels produced showed good internal bond strengths(>0.35 MPa)and met the international standard specifications for interior-grade panels.

A sustainable process to 100%bio-based nylons integrated chemical and biological conversion of lignocellulose

Considerable progress has been made in recent years to the development of sustainable polymers from bio-based feedstocks.In this study,100%bio-based nylons were prepared via an integrated chemical and biological process from lignocellulose.These novel nylons were obtained by the melt polymerization of 3-propyladipic acid derived from lignin and 1,5-pentenediamine/1,4-butanediamine derived from carbohydrate sugar.Central to the concept is a three-step noble metal free catalytic chemical funnelling sequence(Raney Ni mediated reductive catalytic fractionation-reductive funnelling-oxidative funnelling),which allowed for obtaining a single component 3-propyladipic acid from lignin with high efficiency.The structural and thermodynamic properties of the obtained nylons have been systematically investigated,and thus obtained transparent bio-based nylons exhibited higher Mw(>32,000)and excellent thermal stability(Td5%>265℃).Considering their moderate Tg and good melt strength,these transparent bio-based nylons could serve as promising functional additives or temperature-responsive materials.

Recyclable bio-based epoxy resin thermoset polymer from wood for circular economy

Due to their extraordinary durability and thermal stability,Epoxy Resin Thermosets(ERTs)are essential in various industries.However,their poor recyclability leads to unacceptable environmental pollution.In this study,Wu et al.successfully synthesized a completely bio-based ERT using lignocellulose-derived building blocks which exhibit outstanding thermal and mechanical properties.Remarkably,these bio-materials degrade via methanolysis without the need of any catalyst,presenting a smart and cost-effective recycling strategy.Furthermore,this approach could be employed for fabricating reusable composites comprising glass fiber and plant fiber,thereby expanding its applications in sustainable transportation,coatings,paints or biomedical devices.

Bio-based rejuvenators in asphalt pavements:A comprehensive review and analytical study

The pressing demand for sustainable advancements in road infrastructure has catalyzed extensive research into environmentally conscious alternatives for the maintenance and restoration of asphalt concrete pavements.This paper offers a comprehensive review and analysis of bio-based rejuvenators as a promising avenue for enhancing the longevity and sustainability of asphalt.Through a multifaceted exploration,it delves into various aspects of this innovative approach.Providing a thorough overview of bio-based rejuvenators,the study highlights their renewable and environmentally friendly characteristics.It conducts an in-depth examination of a wide spectrum of bio-derived materials,including vegetable oils,waste-derived bio-products,and biopolymers,through a comprehensive survey.The paper evaluates how bio-based rejuvenators enhance aged asphalt binders and mixes,effectively mitigating the adverse impacts of aging.Furthermore,it investigates how these rejuvenators address environmental concerns by identifying compatibility issues,assessing long-term performance,and evaluating economic feasibility.Finally,the paper outlines potential advancements and research pathways aimed at optimizing the utilization of bio-based rejuvenators in asphalt concrete,thereby contributing to the sustainable evolution of road infrastructure.

Aqueous-phase reforming of hydroxyacetone solution to bio-based H_(2)over supported Pt catalysts

Aqueous-phase reforming(APR)is an attractive process to produce bio-based hydrogen from waste biomass streams,during which the catalyst stability is often challenged due to the harsh reaction conditions.In this work,three Pt-based catalysts supported on C,AlO(OH),and ZrO_(2)were investigated for the APR of hydroxyacetone solution in afixed bed reactor at 225℃and 35 bar.Among them,the Pt/C catalyst showed the highest turnover frequency for H_(2)production(TOF of 8.9 molH_(2)molPt^(-1)min^(-1))and the longest catalyst stability.Over the AlO(OH)and ZrO_(2)supported Pt catalysts,the side reactions consuming H_(2),formation of coke,and Pt sintering result in a low H_(2)production and the fast catalyst deactivation.The proposed reaction pathways suggest that a promising APR catalyst should reform all oxygenates in the aqueous phase,minimize the hydrogenation of the oxygenates,maximize the WGS reaction,and inhibit the condensation and coking reactions for maximizing the hydrogen yield and a stable catalytic performance.

Adhesion of Technical Lignin-Based Non-Isocyanate Polyurethane Adhesives for Wood Bonding

Lignin is the most abundant aromatic natural polymer,and receiving great attention in replacing various petro-leum-based polymers.The aim of this study is to investigate the feasibility of technical lignin as a polyol for the synthesis of non-isocyanate polyurethane(NIPU)adhesives to substitute current polyurethane(PU)adhesives that have been synthesized with toxic isocyanate and polyols.Crude hardwood kraft lignin(C-HKL)was extracted from black liquor from a pulp mill followed by acetone fractionation to obtain acetone soluble-HKL(AS-HKL).Then,C-HKL,AS-HKL,and softwood sodium lignosulfonate(LS)were used for the synthesis of technical lignin-based NIPU adhesives through carbonation and polyamination and silane as a cross-linker.Their adhesion per-formance was determined for plywood.FTIR spectra showed the formation of urethane bonds and the reaction between lignin and silane.The NIPU adhesives prepared with C-HKL showed the highest adhesion strength among the three lignin-based NIPU adhesives.As the silane addition level increased,the adhesion strength of NIPU adhesives increased whereas formaldehyde emission decreased for all NIPU adhesives prepared.These results indicate that NIPU adhesives based on technical kraft lignin have a great potential as polyol for the synth-esis of bio-based NIPU adhesives for wood bonding.

Theoretical optimization of micropillar arrays for structurally stable bioinspired dry adhesives

Inspired by the excellent adhesion performances of setae structure from organisms,micro/nano-pillar array has become one of the paradigms for adhesive surfaces.The micropillar arrays are composed of the resin pillars for adhesion and the substrate with different elastic modulus for supporting.The stress singularity at the bi-material corner between the pillars and the substrate can induce the failure of the micropillar-substrate corner and further hinder the fabrication and application of micropillar arrays,yet the design for the stability of the micropillar array lacks systematical and quantitative guides.In this work,we develop a semi-analytical method to provide the full expressions for the stress distribution within the bi-material corner combining analytical derivations and numerical calculations.The predictions for the stress within the singularity field can be obtained based on the full expressions of the stress.The good agreement between the predictions and the FEM results demonstrates the high reliability of our method.By adopting the strain energy density factor approach,the stability of the pillar-substrate corner is assessed by predicting the failure at the corner.For the elastic mismatch between the pillar and substrate given in this paper,the stability can be improved by increasing the ratio of the shear modulus of the substrate to that of the micropillar.Our study provides accurate predictions for the stress distribution at the bi-material corner and can guide the optimization of material combinations of the pillars and the substrate for more stable bioinspired dry adhesives.

Mussel-inspired Methacrylic Gelatin-dopamine/Ag Nanoparticles/Graphene Oxide Hydrogels with Improved Adhesive and Antibacterial Properties for Applications as Wound Dressings

A novel strategy was developed to prepare the methacrylic gelatin-dopamine(GelMA-DA)/Ag nanoparticles(NPs)/graphene oxide(GO) composite hydrogels with good biocompatibility,mechanical properties,and antibacterial activity.Mussel-inspired DA was utilized to modify the GelMA molecules,which imparts good adhesive performance to the hydrogels.GO,interfacial enhancer,not only improves mechanical properties of the hydrogels,but also provides anchor sites for loading Ag NPs through numerous oxygencontaining functional groups on the surface.The experimental results show that the GelMA/Ag NPs/GO hydrogels have good biocompatibility,and exhibit a swelling rate of 202±16%,the lap shear strength of 147±17 kPa,and compressive modulus of 136±53 kPa,in the case of the Ag NPs/GO content of 2 mg/mL.Antibacterial activity of the hydrogels against both gram-negative and gram-positive bacteria is dependent on the Ag NPs/GO content derived from the release of Ag^(+).Furthermore,the GelMA/Ag NPs/GO hydrogels possess good adhesive ability,which is resistant to highly twisted state when stuck on the surface of pigskin.These results demonstrate promising potential of the GelMA-DA/Ag NPs/GO hydrogels as wound dressings for biomedical applications in clinical and emergent treatment.

Universal Encapsulation Adhesive for Lead Sedimentation and Attachable Perovskite Solar Cells with Enhanced Performance

In this work,a modified polyurethane adhesive(PUA)was prepared to realize a convenient encapsulation strategy for lead sedimentation and attachable perovskite solar cells(A-PSCs).The modified PUA can completely self-heal within 45 min at room temperature with an efficient lead ion-blocking rate of 99.3%.The PUA film can be coated on a metal electrode with slight efficiency improvement from 23.96%to 24.15%.The thermal stability at 65℃and the humidity stability at 55%relative humidity(RH)are superior to the devices encapsulated with polyisobutylene.The PUA film has strong adhesion to the flexible substrate and the initial efficiency of the flexible perovskite module(17.2%)encapsulated by PUA remains 92.6%within 1825 h.These results suggest that PUA encapsulation is universal for rigid and flexible PSCs with enhanced stability and low lead hazards.Moreover,it was found that flexible PSCs can be well attached to various substrates with PUA,providing a facile route for the A-PSCs in various scenarios without additional encapsulation and installation.

Effect of Adhesive Type on the Quality of Coconut Shell Charcoal Briquettes Prepared by the Screw Extruder Machine

Indonesia is one of the largest coconut-producing countries in the world.The utilization of coconut shell waste into briquettes will increase the selling value and become a great export opportunity.However,the effect of adhesives on the quality of coconut shell charcoal briquettes made using screw extruder machine has not been widely studied.This study aims to determine the effect of adhesive type on the quality of coconut shell charcoal briquettes.The process of fabricating briquettes in this study included crushing,mixing,blending,pressing,and drying.In the mixing process,3 types of adhesives were used,namely tapioca flour(Briquette_1),cassava flour(Briquette_2),and modified cassava flour(Briquette_3)with a concentration of 5%of the weight of coconut shell charcoal powders.The quality of the resulting briquettes and commercial briquettes will be evaluated by moisture content,ash content,volatile matter,fixed carbon,calorific value,density,compressive,and drop test testing.The results of this research showed that the type of adhesive had a significant effect on the quality of the briquettes produced.Specimen Briquette_1 had better quality than commercial briquettes(Briquette_4)and other briquette specimens.The test results showed that Briquette_1 produced briquettes with better compressive strength and friability than the other specimens,at 6.95 N/mm^(2) and 4.44%,respectively.The moisture content,ash content,fixed carbon,and calorific value of Briquette_1 have met the requirements set by the Indonesian National Standard(SNI)number 01-6235-2000.Meanwhile,the volatile matter content and density of Briquette_1 are by the standards of Japan and the United States America(USA).

Preparation of Environmentally Friendly Urea-Hexanediamine-Glyoxal(HUG)Resin Wood Adhesive

Using non-toxic,low-volatile glyoxal to completely replace formaldehyde for preparing urea-glyoxal(UG)resin adhesive is a hot research topic that could be of great interest for the wood industry.However,urea-glyoxal(UG)resins prepared by just using glyoxal instead of formaldehyde usually yields a lower degree of polymerization.This results in a poorer bonding performance and water resistance of UG resins.A good solution is to pre-react urea to preform polyurea molecules presenting already a certain degree of polymerization,and then to condense these with glyoxal to obtain a novel UG resin.Therefore,in this present work,the urea was reacted with hexamethylene diamine to form a polyurea named HU,and then this was used to react it with different amounts of glyoxal to synthesize hexamethylenediamine-urea-glyoxal(HUG)polycondensation resins,and to use this for bonding plywood.The results show that the glyoxal can well react with HU polyuria via addition and schiff base reaction,and also the HUG resin exhibits excellent bonding strength and water resistance.The shear strength of the plywood bonded with this HUG at 160°C hot press temperature as high as 1.93 MPa,2.16 MPa and 1.61 MPa,respectively,which meets the requirement of the China national standard GB/T 9846-2015(≥0.7 MPa),and can be a good choice as a wood adhesive for industrial application.

Efficacy of Cyanoacrylate Tissue Adhesive Application in the Management of Corneal Perforations at Preah Ang Duong Hospital in Cambodia

Purpose: The study was to evaluate the efficacy of cyanoacrylate tissue adhesive (CTA) application in corneal perforations. Method: This was a prospective study on 20 patients of corneal perforations who received cyanoacrylate tissue adhesive application as treatment between March 2021 and March 2022 at Preah Ang Duong Hospital. The primary outcome measure was success rate of CTA application, while the secondary outcome was to measure postoperative best-corrected visual acuity (BCVA) and ocular complications. Results: The mean age of patients was 44.15 ± 16.05 years old and 7 (35%) were female. Causes of perforation were microbial infection in 12 patients (60%), trauma in 5 patients (25%), and sterile melting in 3 patients (15%). The perforation of size smaller than 1.5 mm was in 8 patients (40%) while 12 patients (60%) had perforated size between 1.5 mm to 3 mm. The perforation was 60% (12 patients) central, 25% (5 patients) paracentral, and 15% (3 patients) peripherally. Out of 20 patients, 5 patients (25%) received CTA application more than 1 time. The mean glue retention was 57.60 ± 31.84 days. Success rate of glue application (defined as intact globe without surgical intervention regardless of number of CTA applications) was 85%. At the last visit, 7 patients (35%) had BCVA of 6/120 or better. Common complications were uveitis (45%), ocular hypertension (30%), cataract (25%) and neovascularization (20%). No serious complications were found. Conclusion: Cyanoacrylate tissue adhesive is an effective treatment option in sealing corneal perforations with no serious complications. .

Termite Resistance of Heat-Treated Eucalyptus OSB Bonded with Eco-Friendly Castor Oil Adhesive

Over the last decade,the oriented strand board(OSB)market presented meaningful growth.However,as a woodbased product,because of its anatomical structure and chemical composition,OSB can be damaged by biodeterioration agents.Given that,the biodeterioration of OSB panels must be investigated to improve its durability.In this way,this work analyses the biological resistance against termites(Cryptotermes brevis and Nasutitermes corniger)of heat-treated OSB panels made with Eucalyptus wood glued with vegetable-based polyurethane-an ecofriendly and sustainable adhesive derived from castor oil.Various panels were produced with different layers compositions(face:core:face of 25:50:25 and 30:40:30)in wood mass proportion and were submitted to postproduction heat treatment(at 175℃ and 200℃)replacing the use of chemical insecticides.The influence of the layers variation and heat treatment temperature were evaluated,and these results were compared with commercial panels(made from pinus wood with insecticide).The results showed that the heat treatment did not improve the resistance against termite attack.However,all the experimental panels presented a satisfactory performance that was compatible with the commercial panels produced with insecticide available in the Brazilian market.The combination of Eucalyptus wood and castor oil adhesive to produce OSB,in any variation of layer composition,demonstrated natural resistance against termite attack compatible with the commercial panels,even without using chemical additives to increase durability.

Properties of Bark Particleboard Bonded with Demethylated Lignin Adhesives Derived from Leucaena leucocephala Bark

Lignin extraction from bark can maximize the utilization of biomass waste,offer cost-effectiveness,and promote environmental friendliness when employed as an adhesive material in bark particleboard production.Particles of fine(0.2 to 1.0 mm),medium(1.0 to 2.5 mm),and coarse(2.5 to 12.0 mm)sizes,derived from the bark of Leucaena leucocephala,were hot-pressed using a heating plate at 175℃for 7 min to create single-layer particleboards measuring 320 mm×320 mm×10 mm,targeting a density of 700 kg/m^(3).Subsequently,the samples were trimmed and conditioned at 20℃and 65%relative humidity.In this study,we compared bark particleboard bonded with urea formaldehyde(UF)adhesive to fine-sized particleboard bonded with demethylated lignin adhesive.The results indicated that bark particleboards utilizing demethylated lignin and UF adhesives exhibited similar qualities.Coarse particleboard showed differences in modulus of elasticity(MOE)and modulus of rupture(MOR),while medium-sized particles exhibited significant variations in moisture content(MC)and water absorption(WA).Furthermore,the thickness swelling of coarse and medium-sized particles under wet and oven-dried conditions exhibited notable distinctions.Overall,the demethylated lignin adhesive extracted from L.leucocephala bark demonstrated similar quality to UF adhesive,with particle size correlating inversely to the strength of the bark particleboard.

Endoscopic band ligation or endoscopic tissue adhesive injection in the treatment of gastric varices:Which is better?

The combination of endoscopic ultrasound with endoscopic treatment of type 1 gastric variceal hemorrhage may improve the robustness and generalizability of the findings in future studies.Moreover,the esophageal varices should also be included in the evaluation of treatment efficacy in subsequent studies to reach a more convincing conclusion.

Ginger oil-loaded transdermal adhesive patch treats post-traumatic stress disorder

Objective:To find a viable alternative to reduce the number of doses required for the patients with post-traumatic stress disorder(PTSD),and to improve efficacy and patient compliance.Methods: In this study,we used ginger oil,a phytochemical with potential therapeutic properties,to prepare ginger oil patches.High-performance liquid chromatography(HPLC)was used to quantify the main active component of ginger oil,6-gingerol.Transdermal absorption experiments were conducted to optimize the various pressure-sensitive adhesives and permeation enhancers,including their type and concentration.Subsequently,the ginger oil patches were optimized and subjected to content determination and property evaluations.A PTSD mouse model was established using the foot-shock method.The therapeutic effect of ginger oil patches on PTSD was assessed through pathological sections,behavioral tests,and the evaluation of biomarkers such as tumor necrosis factor-α(TNF-α),interleukin-6(IL-6),brain-derived neurotrophic factor(BDNF),and melatonin(MT).Results: The results demonstrated that ginger oil patches exerted therapeutic effects against PTSD by inhibiting inflammatory responses and modulating MT and BDNF levels.Pharmacokinetic experiments revealed that ginger oil patches maintained a stable blood drug concentration for at least one day,addressing the rapid metabolism drawback of 6-gingerol and enhancing its therapeutic efficacy.Conclusions: Ginger oil can be prepared as a transdermal drug patch that meets these requirements,and the bioavailability of the prepared patch is better than that of oral administration.It can improve PTSD with good patient compliance and ease of administration.Therefore,it is a promising therapeutic formulation for the treatment of PTSD.

Investigating the Mechanical and Thermal Properties of PDMS-Toughened Epoxy Resins for Advanced Adhesive Solutions

This study investigates the enhancement of mechanical and thermal properties in epoxy resins modified with polydimethylsiloxane (PDMS) for advanced adhesive applications. The research focuses on evaluating the tensile strength, thermal stability, and glass transition temperature (Tg) of PDMS-toughened epoxy resins. The primary objective of this study was to explore the use of polydimethylsiloxane (PDMS) as an impact modifier for epoxy resin. We successfully synthesized a grafting copolymer of diglycidyl ether bisphenol-A (DGEBA) and hydroxyl-terminated polydimethylsiloxane (HTPDMS) through the condensation of hydroxyl groups. Triethylene tetraamine (TETA) was employed as the curing agent to cross-link both DGEBA and the HTPDMS copolymer. The chemical structure of the DGEBA-HTPDMS grafting copolymer was confirmed using fourier transform infrared (FT-IR) spectroscopy and 1H nuclear magnetic resonance (NMR) spectroscopy. Tensile testing of the cured materials indicated that the elongation at break increased upon addition of PDMS. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) revealed improved thermal stability for the DGEBA system with the incorporation of HTPDMS. These findings suggest that the Si-O-Si segments within the PDMS contribute to the improved mechanical and thermal properties of the DGEBA-based resin.