Color and Gloss Changes of a Lignin-Based Polyurethane Coating under Accelerated Weathering

The purpose of this research study was to investigate the properties of polyurethane coatings based on lignin nano-particles.For this purpose,the prepared coatings were applied to pine wood surfaces and weathered artificially.Subsequently,color and gloss of the coatings were measured before and after the weathering test.Field emission scanning electron microscopy(FE-SEM)micrographs prepared from the coatings showed that the average size of nano-particles in the polyurethane substrate was approximately 500 nm.Nuclear magnetic resonance(13C-NMR)spectroscopy showed that strong urethane bonds were formed in the nano-lignin-based polyurethane.Differential calorimetric analysis(DSC)test revealed that the glass-transition temperature(Tg)of lignin nanoparticles modified with diethylenetriamine(DETA)was 112.8℃ and Tg of lignin nano-particles modified with ethylenediamine(EDA)was 102.5℃,which is lower than the Tg of un-modified lignin(114.6℃)and lignin modified with DETA(126.8℃)and lignin modified with EDA(131.3℃).The coatings modified with lignin nano-particles had a greater change in gloss.The lignin nano-particles in the modified coating are trapping hydroxyl radicals which reduces photoactivity and yellowing of the polyurethane by about 3 times compared to unmodified polyurethane coatings.After weathering test,the nano-lignin-based coating had a rougher surface with a lower contact angle(0.78°)compared to the unmodified polyurethane coating(0.85°).

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.

Matrix Assisted Laser Desorption Ionization Time of Flight(MALDI-TOF)-Mass Spectrometry and^(13)C-NMR-Identified New Compounds in Paraberlinia bifoliolata(Ekop-Beli)Bark Tannins

Extracts of plant origin,particularly tannins,are attracting growing interest for the sustainable development of materials in the industrial sector.The discovery of new tannins is therefore necessary.The aim of this work was to contribute to the understanding of the properties of Paraberlinia bifoliolata tannin by Matrix Assisted Laser Desorption Ionization Time of Flight Mass Spectroscopy MALDI-TOF/MS and Carbon 13 Nuclear Magnetic Resonance(13C NMR).The chemical composition of tannin extracted from Paraberlinia bifoliolata bark was determined,as was the mechanical strength of the resin hardened with Acacia nilotica extracts.Yield by successive water extraction was 35%.MALDI-TOF/MS analysis revealed the presence of three new compounds in this tannin,previously unknown in this family of extracts.These are 3-hydroxyproline acid,N-methyl-4-hydroxypipecolic acid and N-methyl-5-dihydroxypipecolic acid.The identification of the above molecules means that this tannin can be used for industrial applications,as a resin in the manufacture of particleboard and in the formulation of green corrosion inhibitors.This information is reinforced by 13C NMR spectrometry,which indicates the presence of several polyflavonoid units,confirming the condensed nature of the tannin.Thermomechanical analysis of the resin formed by the purified tannin of Paraberlinia bifoliolata to which a vegetal biohardener has been added provided a Modulus of Elasticity(MOE)value of 4840 MPa at 150℃,confirming its possible use as a binder resin in the manufacture of wood panels as well as for the formulation of a corrosion inhibitor.

A Review on Sources,Extractions and Analysis Methods of a Sustainable Biomaterial:Tannins

Condensed and hydrolysable tannins are non-toxic natural polyphenols that are a commercial commodity industrialized for tanning hides to obtain leather and for a growing number of other industrial applications mainly to substitute petroleum-based products.They are a definite class of sustainable materials of the forestry industry.They have been in operation for hundreds of years to manufacture leather and now for a growing number of applications in a variety of other industries,such as wood adhesives,metal coating,pharmaceutical/medical applications and several others.This review presents the main sources,either already or potentially commercial of this forestry by-materials,their industrial and laboratory extraction systems,their systems of analysis with their advantages and drawbacks,be these methods so simple to even appear primitive but nonetheless of proven effectiveness,or very modern and instrumental.It constitutes a basic but essential summary of what is necessary to know of these sustainable materials.In doing so,the review highlights some of the main challenges that remain to be addressed to deliver the quality and economics of tannin supply necessary to fulfill the industrial production requirements for some materials-based uses.

Numerical Modeling and Technico-Economic Analysis of a Hybrid Energy Production System for Self-Consumption: Case of Rural Area in the Comoros

This study aims to provide electricity to a remote village in the Union of Comoros that has been affected by energy problems for over 40 years. The study uses a 50 kW diesel generator, a 10 kW wind turbine, 1500 kW photovoltaic solar panels, a converter, and storage batteries as the proposed sources. The main objective of this study is to conduct a detailed analysis and optimization of a hybrid diesel and renewable energy system to meet the electricity demand of a remote area village of 800 to 1500 inhabitants located in the north of Ngazidja Island in Comoros. The study uses the Hybrid Optimization Model for Electric Renewable (HOMER) Pro to conduct simulations and optimize the analysis using meteorological data from Comoros. The results show that hybrid combination is more profitable in terms of margin on economic cost with a less expensive investment. With a diesel cost of $1/L, an average wind speed of 5.09 m/s and a solar irradiation value of 6.14 kWh/m2/day, the system works well with a proportion of renewable energy production of 99.44% with an emission quantity of 1311.407 kg/year. 99.2% of the production comes from renewable sources with an estimated energy surplus of 2,125,344 kWh/year with the cost of electricity (COE) estimated at $0.18/kWh, presenting a cost-effective alternative compared to current market rates. These results present better optimization of the used hybrid energy system, satisfying energy demand and reducing the environmental impact.

Hydrolysable Chestnut Tannin Extract Chemical Complexity in Its Reactions for Non-Isocyanate Polyurethanes(NIPU)Foams

Non-isocyanate polyurethane(NIPU)foams from a commercial hydrolysable tannin extract,chestnut wood tannin extract,have been prepared to determine what chemical species and products are taking part in the reactions involved.This method is based on two main steps:the reaction with dimethyl carbonate and the formation of urethane bonds by further reaction of the carbonated tannin with a diamine-like hexamethylene diamine.The hydroxyl groups on the tannin polyphenols and on the carbohydrates intimately linked with it and part of a hydrolysable tannin are the groups involved in these reactions.The carbohydrate skeleton of the hydrolysable tannin is also able to participate through its hydroxyl groups to the same two reactions rendering the whole molecular complex able to react to form NIPUs.The analysis by Matrix-Assisted Laser Desorption Ionization(MALDI-TOF)mass spectrometry and 13C Nuclear Magnetic Resonance(13C NMR)to further investigate the reaction mechanisms involved revealed the unsuspected complexity of chestnut hydrolysable tannin,with different fragments reacting in different manners forming a hardened network of considerable complexity.As the morphology and performance of these types of foams changes slightly with the change in the amount of glutaraldehyde and hexamine hardeners,the best performing foam formulation previously determined was scanned by SEM and analysed chemically for the structures formed.

Little Secrets for the Successful Industrial Use of Tannin Adhesives:A Review

This brief article reviews a very particular and quite narrowfield,namely what has been done and what is needed to know for tannin adhesives for wood panels to succeed industrially.The present fashionable focus on bioadhe-sives has led to producing chemical adhesive formulations and approaches for tannin adhesives as a subject of academic publications.These,as good and original they might be,are and will still remain a rather empty aca-demic exercise if not put to the test of real industrial trials and industrial use.They will remain so without the“little”secrets and techniques outlined here that show that there is a great gap between developing an adhesive formulation in the laboratory and the hard reality to make it work where it does really count,in its industrial application.It outlines the fact that even more modern and excellent,newly developed bioadhesive formulations might well miserably fail once tried in the industry if the problems that always arise in their upgrading are not identified and solved,and solved well.It also outlines the fact that not only must costs always be taken into account and that a practical and possibly easy-to-handle approach must always be used,but too expensive or complex and unyielding adhesive systems are also often shown to be unusable or unsuitable in industry.

Effect of Amine Type on Lignin Modification to Evaluate Its Reactivity in Polyol Construction for Non-Isocyanate Polyurethanes(NIPU)

Polyols are groups of organic compounds which contain carbon and are randomly linked to other atoms,especially carbon-carbon and carbon-hydrogen.These compounds are mainly used as reactants to make other polymers.Among biopolymers,lignin is regarded as the base of a new polymer in polyol construction.The present study aimed to investigate the effects of amine type(diethylenetriamine and ethylenediamine)on the modification of lignin-based polyols,so as to provide an alternative to petroleum polyols and,in turn,increase functional groups and reduce their harm to humans’health and the environment.To this aim,first,lignin was extracted from raw liquor.Next,the extracted lignin was reacted with diethylenetriamine(DETA)and ethylenediamine(EDA).Finally,the Mannich method was used for the reaction between amine lignin and propylene carbonate.The results of the Fourier Transform Infrared(FTIR)spectroscopy analysis showed that modification with DETA led to more structural change in lignin and peak 1100 indicates the presence of C–O bond related to urethane bonds in modified lignin.Moreover,adding propylene carbonate to aminated lignin did not result in much change in the results of the FTIR analysis.Additionally,urethane bonds can be seen in the results of GPC at 400℃–500℃.Furthermore,a slight decrease in thermal stability was observed in lignin modified with amine and propylene carbonate,compared to the raw lignin sample.

Self-Cross-Linked Tannin-Aminated Tannin Surface Coatings for Particleboard

Aminated tannins were prepared by reacting mimosa condensed tannin extract with ammonia yielding the substitution of many,if not all of the tannin hydroxyl groups with–NH_(2)groups.A tannin-aminated tannin(ATT)particleboard coating was then prepared by reacting raw tannin extract with aminated tannin extract and thus cross-linking the two by substituting tannin’s hydroxyl groups with the–NH_(2)groups on the aminated tannin to form–NH-bridges between the two.The resulting particleboard coating gave encouraging results when pressed at 180℃for 3 min.Conversely,the system in which tannin was reacted/cross-liked with urea(ATU)by a similar amination reaction did not perform as well as the ATT system,and this even when a higher curing temperature and longer hot press time were used.In particular its water repellence was worse probably due to the presence of urea and such a system with lower reactivity.Nonetheless,substituting the tannin–OHs with the urea–NH_(2)groups appeared to also take place.ATT gave better results than ATU as regards water repellence and mechanical resistance as shown by the cross cut test.The ATT system was shown to be between 95%and 98%biosourced.The difference appeared to be due,by TMA analysis,to the much faster formation of the ATT hardened network leading to a better cross-linked polymer coating.The chemical species formed for both the ATT and ATU system were studied by MALDI ToF and CP MAS^(13)C NMR.

Nanolignin,a Coupling Bio-Agent for Wood-Plastic Composites

The influence of nanolignin coupling bio-agent on some characteristics of polypropylene-wood flour composites was studied.Thus,nanolignin was prepared by the acidic method,and then different ratios of it(0,1,3 and 5 wt%)were added to a polypropylene-wood flour mixture.After mechanically mixing wood flour,nanolignin,and polypropylene,the mixture was injection molded.ASTM methods were used to measure the structural properties of nanolignin,and prepared composites’water absorption,thickness swelling,bending modulus,and bending,tensile and impact strengths.Transforming the original lignin to nanolignin did not change the chemical bonds of the material.The addition of nanolignin yielded improved mechanical and physical properties of the composites prepared.Higher strength and dimensional stability are presented by nanolignin-containing composites when comparing them with those prepared with normal lignin.Nanolignin was shown by SEM(Scanning Electron Microscope)observation to be uniformly dispersed within the polymer matrix.Wood polymer composites(WPCs)with nanolignin exhibited comparable properties with the control samples prepared using maleic anhydride polypropylene(MAPP).

A Methodology to Reduce Thermal Gradients Due to the Exothermic Reactions in Resin Transfer Molding Applications

Resin transfer molding(RTM)is among the most used manufacturing processes for composite parts.Initially,the resin cure is initiated by heat supply to the mold.The supplementary heat generated during the reaction can cause thermal gradients in the composite,potentially leading to undesired residual stresses which can cause shrinkage and warpage.In the present numerical study of these processes,a one-dimensional finite difference method is used to predict the temperature evolution and the degree of cure in the course of the resin polymerization;the effect of some parameters on the thermal gradient is then analyzed,namely:the fiber nature,the use of multiple layers of reinforcement with different thermal properties and also the temperature cycle variation.The validity of this numerical model is tested by comparison with experimental and numerical results in the existing literature.

A Melamine–Dialdehyde Starch Wood Particleboard Surface Finish without Formaldehyde

Melamine-dialdehyde starch resins used for wood surface finishes have been developed.The reaction of melamine with dialdehyde starch has been shown to occur by FTIR and MALDI ToF spectrometry,with several oligomer species due to the reaction of the two materials being identified,and the resin thermal stability was studied by thermogravimetric analysis.The resins were prepared by two different procedures when it was realized that dialdehyde starch is sensitive to too high a temperature for prolonged times.The melamine-dialdehyde starch resins were applied on particleboard supports as a direct liquid surface finish and a resin-impregnated paper.The surface finishes were tested for adhesion by the cross-cut test,their initial sessile drop contact angle,and the contact angle evolution as a function of time.The best results were obtained by the resins catalyzed by 2% ammonium sulfate and applied to the support surface as a resin-impregnated paper hot pressed for 3 min at 200℃,although the results at 180℃ also looked promising.

Modification of Wood by Tannin-Furfuryl Alcohol Resins-Effect on Dimensional Stability,Mechanical Properties and Decay Durability

Furfurylation is a well-known wood modification technology.This paper studied the effect of tannin addition on the wood furfurylation.Three kinds of dicarboxylic acids,adipic acid,succinic acid,and tartaric acid,as well as glyoxal as a comparing agent,were used to catalyse the polymerisation of furanic or tannin-furanic solutions during wood modification.Impregnation of furanic or tannin-furanic solution at a certain concentration into the wood followed with curing at 103℃for a specific duration was performed for the wood modification.Different properties of the modified woods like dimensional stability,resistance of treatment to leaching,mechanical properties,decay durability against white-rot(Coriolus versicolor,Pycnoporus sanguineus)and brown-rot(Coniophora puteana)as well as their chemical and anatomical characteristics were evaluated.Results revealed that the partial substitution of FA by the tannins improved the fixation of the chemicals impregnated in wood.Further,dimensional stability,leaching resistance,Brinell hardness,modulus of elasticity/modulus of rupture,and decay durability properties of the furfurylated wood were also improved in the presence of tannins.Scanning electron microscopy revealed the deposition of the polymer in the wood lumen cells and in the wood cell walls.

A Comparative Study of Different Drying Processes for a Deformable Saturated Porous Medium

Drying of a deformable saturated porous medium based on convective tempering is a novel method that can enhance energy efficiency and the quality of the dried product itself.In this experimental investigation,the performances of this specific technique are compared with those of a standard stationary drying process in terms of deformation,drying kinetics,moisture redistribution,and energy consumption.In particular,the response of a deformable saturated porous medium(Kaolin)is considered.The results are critically discussed pointing out advantages and drawbacks.

Numerical Study on the Resin Transfer Molding Curing Process for Thick Composites Materials

The successful manufacture of thick composites is challenging since the highly exothermic nature of thermoset resins and limited temperature control make avoiding the onset of detrimental thermal gradients within the composite relatively difficult.This phenomenon is mainly caused by exothermic heat reactions.The so-called Michaud's model has been largely used in the literature to reduce the gap between experience and simulation with regard to the effective prediction of the temperature cycle in these processes.In this work,another solution is proposed to simulate the curing process for thick composites,namely preheating the resin to activate the curing reaction before resin injection into the mold.A good agreement between the experiment and the simulation is found.Moreover,in order to minimize the thermal gradient in the final composite,the thermophysical properties of the fiber and the torque(temperature,time)of the Plate have been varied leading to interesting results.

Performance of a Solar-Biomass Adsorption Chiller

A dynamic model is presented for a chiller working with a composite adsorbent(silica activated carbon/CaCl2)–water pair in a solar-biomass cooling installation.The main objective is determining a link between two possible evaporator configurations and the refrigerator’s performances.The two considered evaporators work at different pressure levels.The related time evolution profiles of temperature,pressure and water content are studied.Moreover,the effects of hot water inlet temperature and cooling water inlet temperature on the specific cooling capacity(SCP)and coefficient of performance(COP)are predicted by means of numerical simulations.The results show that an increase in the temperature of hot water and a decrease in the temperature of the cooling water allow an increase in COP and SCP.In particular,for a hot water inlet temperature of 85°C and a cooling water inlet temperature of 40°C,the COP and Qev are 0.67 and 4.3 kW,respectively.

Static Bending Creep Properties of Glass Fiber Surface Composite Wood

To study the static bending creep properties of glass fiber reinforced wood,glass fiber reinforced poplar(GFRP)specimens were obtained by pasting glass fiber on the upper and lower surfaces of Poplar(Populus euramevicana,P),the performance of Normal Creep(NC)and Mechanical Sorptive Creep(MSC)of GFRP and their influencing factors were tested and analyzed.The test results and analysis show that:(1)The MOE and MOR of Poplar were increased by 17.06%and 10.00%respectively by the glass fiber surface reinforced composite.(2)The surface reinforced P with glass fiber cloth only exhibits the NC pattern of wood and loses the MSC characteristics of wood,regardless of the constant or alternating changes in relative humidity.(3)The instantaneous elastic deformation,viscoelastic deformation,viscous deformation and total creep deflection of GFRP are positively correlated with the stress level of the external load applied to the specimen.Still,the specimen’s creep recovery rate is negatively correlated with the stress level of the external load applied to the specimen.The static creep deflection and viscous deformation of GFRP increase with the increase of the relative humidity of the environment.(4)The MSC maximum creep deflection of GFRP increased by only 7.41%over the NC maximum creep deflection,but the MSC maximum creep deflection of P increased by 199.25%over the NC maximum creep deflection.(5)The Burgers 4-factor model and the Weibull distribution equation can fit the NC and NC recovery processes of GFRP well.

MUF Resins Improved by Citric Acid as Adhesives for Wood Veneer Panels

This article presents the first applied results of using citric acid in combinations with a melamine-urea-formal-dehyde(MUF)resin for bonding wood veneers.The chemical reactions involved are shown based on a MALDI ToF analysis of the reaction of the MUF resin with citric acid.The preliminary results of the physical and mechanical properties of the LVL prepared are also presented.Veneers from Populus sp were used to manufacture 5-layer laminated veneer lumber(LVL)of small dimensions.Five combinations of the amount of citric acid,MUF spread rate and pressing parameters were tested.LVL bonded with 20%of citric acid+100 g/m^(2)of MUF,hot-pressed using a 3-step process with maximum 1.5 MPa of pressure yielded the board with better dimensional stability and mechanical properties.It could be concluded that citric acid in combination with MUF can be used for bonding wood veneer and the research should be continued to study further the parameters involved and to enhance the results.

Flexible Biofoams Based on Furanics and Fatty Acids Esterified Tannin

Water repellant,flexible biofoams using tannin esterified with various fatty acid chains,namely lauric,palmitic and oleic acids,by reaction with lauryl chloride,palmitoyl chloride,and oleyl chloride were developed and their characteristics compared with the equivalently esterified rigid biofoams.Glycerol,while initially added to control the reaction temperature,was used as a plasticizer yielding flexible biofoams presenting the same water repellant character that the equivalent rigid foams.Acetaldehyde was used as the cross-linking agent instead of formaldehyde,as it showed a better performance with the esterified tannin.The compression results showed a significant decrease of the Modulus of Elasticity(MOE)of the flexible foams in relation to that of the rigid foams,confirming their flexible character.The lauryl-and palmitoyl-esterified biofoams presented similar mechanical properties,while the oleyl-esterified biofoam presented different mechanical and morphological result not really showing the expected flexibility.Both the esterified rigid and flexible tannin-based biofoams showed good water resistance and their sessile drop contact angle analysis as a function of time confirmed this characteristic.Scanning Electron Microscope(SEM)analysis showed the flexible foams to present a higher proportion of closed cells than the rigid foams.Conversely,the cells depth of the flexible foams was lower than that of the rigid foam.As regards their thermal resistance,the flexible foams showed a slight loss of mass compared to the rigid ones without glycerol.Both types of foams presented much lower surface friability of non-esterified rigid foams.

室外涂饰木材的抗老化性能

通过测量气体渗透值研究室外涂饰木材在老化过程中的性能表现。结果表明:涂层渗透性与涂料的抗老化能力无直接关系;木材涂饰以后气体渗透值比未涂饰时均有所下降,在老化过程中涂饰木材的气体渗透值随着老化时间的增加而增加。木材径切面上的漆膜比弦切面上的抗老化,径切面上的渗透变化率kt和老化时间的关系为:渗透变化率在老化初期增长趋势很快,随着老化时间的增加逐渐变缓,到老化后期甚至出现渗透变化率下降的趋势。