Source: UNIV OF IDAHO submitted to NRP
HYBRIDIZING WOOD WITH ZINC OXIDE-EUGENOL CEMENT TOWARDS HIGH-PERFORMANCE BUILDING MATERIALS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
ACTIVE
Funding Source
Reporting Frequency
Annual
Accession No.
1026472
Grant No.
2021-67022-34834
Cumulative Award Amt.
$329,888.00
Proposal No.
2020-08740
Multistate No.
(N/A)
Project Start Date
May 1, 2021
Project End Date
Apr 30, 2026
Grant Year
2021
Program Code
[A1531]- Biorefining and Biomanufacturing
Recipient Organization
UNIV OF IDAHO
875 PERIMETER DRIVE
MOSCOW,ID 83844-9803
Performing Department
(N/A)
Non Technical Summary
The overall goal of this project is to develop an environmentally friendly approach for wood protection, with a focus on stabilization of eugenol, a volatile natural antimicrobial compound, with zinc oxide (ZnO), a multifunctional mineral, and promote an in situ incorporation of ZnO-eugenol cement (ZnO-EG) in wood. ZnO-EG cement is an inexpensive dental filling material with strong antimicrobial properties and exceptional mechanical strength. By incorporating it in wood, we will examine all the key factors affecting wood treatment by ZnO-EG cement, which are especially important for industrial applications. These include: (1) hybridize wood with ZnO-EG cement through two-step vacuum impregnation, (2) study the penetrability of ZnO-EG in wood structure by mass gain and bulking as well as Energy Dispersive X-Ray Spectroscopy in conjunction with scanning electron microscopy, (3) test the resistance of ZnO-EG to leaching due to weathering conditions and (4) examine the resistance of ZnO-EG treated wood against brown-rot and white-rot fungi. In addition to the potential increase in the wood durability, we expect that the weathering performance, fire resistance and dimensional stability of ZnO-EG cement hybrid wood will improved due to the inherent UV absorbing characteristic and fire-retardant properties of ZnO, as well as the exceptional mechanical strength of ZnO-EG cement that could bind into the wood cell. This multidisciplinary study involves knowledge from chemistry, microbiology and wood science. Our approach will offer an increased life of wood products that allow for less greenhouse gas emissions, increased carbon storage and better utilization of natural resources.
Animal Health Component
20%
Research Effort Categories
Basic
60%
Applied
20%
Developmental
20%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
12306502020100%
Goals / Objectives
The overall goal of this project is to develop an environmentally friendly approach for wood protection, with a focus on stabilization of eugenol, a volatile natural antimicrobial compound, with zinc oxide (ZnO), a multifunctional mineral, and promote an in situ incorporation of ZnO-eugenol cement (ZnO-EG) in wood. We will:(1) hybridize wood with ZnO-EG cement through two-step vacuum impregnation, (2) study the penetrability of ZnO-EG in wood structure by mass gain and bulking as well as Energy Dispersive X-Ray Spectroscopy in conjunction with scanning electron microscopy, (3) test the resistance of ZnO-EG to leaching due to weathering conditions and (4) examine the resistance of ZnO-EG treated wood against brown-rot and white-rot fungi.
Project Methods
First, ZnO-EG cement will be prepared according to the procedures outline by Bakhori et al., 2019. Succinctly, ZnO and eugenol at a weight ratio of 4:1 will be mixed started by gradually adding the powder (ZnO) to liquid (eugenol) until all materials blended well. The mixture will be allowed to set for 24 h at room conditions and purified by washing with methanol to remove the residual eugenol in the ZnO-EG cement. The washed ZnO-EG cement will be examined by Fourier-transform infrared spectroscopy (FTIR), powder X-Ray Diffraction and scanning electron microscope (SEM) to observe the changes in functional groups, crystalline characteristics and morphology, respectively. In IR spectra, the absence of the hydroxy aromatic group (O-H) stretching at 3520 and 3460 cm-1, as well as the appearance of ring stretching at 1319 cm-1 in the cement, will be used for confirmation of chelating of eugenol with ZnO (Wilson and Mesley, 1972). In XRD spectra, new peaks with spacings at approximately 17.0, 8.8 and 7.0 A will be used as indicators for the presence of a new crystal form (Bakhori et al., 2019; Copeland et al., 1955). In SEM, parallelepiped shapes with about 20:4:1 length-to-width-to-thickness geometries will be identified as zinc eugenolate crystals (Bakhori et al., 2019).Secondly, we will grow ZnO-EG cement In situ in wood, which will involve four steps: (1) Impregnation of nano-ZnO in the wood scaffold to obtain ZnO/wood, (2) immersion of ZnO/wood into a growth solution, including a precursor solution of eugenol and a catalyst of zinc acetate (ZnAc), by vacuum treatment at room conditions for 2 h, (3) conditioning of treated wood in an environmental chamber (25oC and 60% relative humidity) for 24 h and (4) washing the samples with methanol twice to remove unreacted eugenol. Freeze-dried weight gain before and after treatment will be used as an indicator. Although different treatment parameters will be tested, only the samples with the highest mass gain upon removal of unbounded preservatives will be tested for durability, weathering performance, fire retardance and dimensional stability. Twelve replicates of wood samples will be used for each treatment.In the 3rd activity, we will Study the penetrability of ZnO-EG in wood structure. Basically, the freeze-dried mass of the samples before and after the treatment will be measured to calculate the mass gain. Volumetric changes or bulking due to the incorporation of the chemicals into the cell walls will be measured by a caliper. The mass gain and bulking before and after treatment will be calculated. The distribution of the ZnO-EG on cross-sections of the treated wood will be observed by scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectrometer (EDX) mapping of Zn. Zn is a characteristic element in ZnO-EG cement, which will differentiate itself from other components in wood. Examining where ZnO is in the wood will help confirm the presence and distribution of the ZnO-EG cement in wood. Specifically, the microtomed cross-sections of 30 µm thickness will be sputter-coated with platinum (30 nm thick) and examined microscopically at 15 kV. Elemental mapping will be collected at a working distance of 10 mm and the acquisition time of 300 s.Fourth, before exposure to fungi, the long-term performance of ZnO-EG-treated wood will be tested following the leaching procedures described in AWPA Standard E11-16 (AWPA, 2016a). Briefly, half of the fungal decay test samples will be placed into beakers and weighed down to prevent floating. A total of 240 mL of deionized water will be added to each beaker, and the beakers will be placed at room temperature on an orbital shaker rotating at a speed of 100 rpm. After 6, 24, 48 h, and thereafter at 48 h intervals, the leachate will be removed from the beakers, and replaced with 100 mL fresh deionized water. The leaching process will be performed for a total of 14 days. Leachates will be analyzed for zinc using inductively coupled plasma atomic emission spectrometry (ICP-AES) and expressed as ppm zinc for the average leach rate of the six blocks per treatment concentration over time (Clausen et al., 2010). Eugenol leached will be determined directly in aqueous solution by ultraviolet spectroscopy and the measurements will be made at 281 nm (Cai et al., 2020b).The anti-swelling efficiency of treated samples will be evaluated by measuring the volumetric changes during three cycles of drying-wetting tests (Mubarok et al., 2019). Briefly, the freeze-dried samples will be exposed to a 0.1 bar vacuum in deionized water for 30 minutes, followed by ambient pressure in another water tank for 24 hours. Three cycles will be performed and the volumes of both freeze-dried and water-saturated samples in each cycle will be recorded as Vdry and Vwet, respectively. Swelling (S) and anti-swelling efficiency of the samples will be calculated.In activity 5, the efficacy of treated wood against fungi will be determined per the AWPA E22 standard (AWPA, 2016b). The fungi tested in this study will be two brown rot fungi, Gloeophyllum trabeum and Postia placenta, and two white-rot fungi, Trametes versicolor and Irpex lacteus. The agar plugs will be placed on the edges of the wood feeder strips and a lid with a hole loosely filled by cotton will be used to cap the culture bottle, which would allow for air exchange. The bottles will be incubated until the feeder strips are thoroughly covered with fungal mycelium. The freeze-dried samples will be sterilized with gaseous ethylene oxide under vacuum for 24 hours and inoculate with fungi for 4 weeks. Since white-rot fungi tend to degrade softwood relatively slowly, untreated controls of both the softwood used (in this case southern yellow pine) and a medium-density hardwood (sweetgum) will be used to verify the decay capacity of the fungus isolate used. Resistance to decay will be determined by percent mass loss and compression strength loss of the freeze-dried samples before and after the soil block test. Samples with no significant loss in mass and strength as compared to the untreated-and-unexposed samples are considered protected. Twelve replicates for each treatment will be included.Finally, accelerated weathering tests will be performed according to Feist et al., 1991. The test samples will be exposed to a 6500 W UV light in an enclosed chamber at 45 degree C and relative humidity of 50% for 4 weeks. The 24-hour weathering cycle will consist of 20 h of light with 4 h of distilled water spray. Color changes in the test samples will be determined in the CIE L*a*b* color space by a colorimeter (FRU model WR-10QC). Herein, L* means the lightness from black (0) to white (100) while a* and b* represents chromaticity indices where +a* is red, -a* is green, +b* is yellow and -b* is blue. The total color difference (ΔE*) will be defined. The fire resistance properties of the treated wood will be evaluated according to ASTM E2102-17 standard (ASTM International, 2017) with minor modification, of which the samples size of 25 mm × 18 mm × 18 mm (L × R × T) will be used. Time to ignition, mass loss rate, heat release rate and peak heat release rate will be measured. The reduction in heat release rate will be used as an indicator of the effectiveness of the treatment.

Progress 05/01/23 to 04/30/24

Outputs
Target Audience:One Ph.D. student from under under-representative minority groups Students (2) who were taking FSP 550 Biomaterial Deterioration and Protection course at the University of Idaho: both graduate students Students (4) who were taking FSP 201 Biomaterial Deterioration and Protection course at the University of Idaho: both graduate students Students (~25) who were taking ENVS 300 (s) Environmental Sci Seminar at the University of Idaho: including 3 Moscow high school students Changes/Problems:A non-cost extension request was approved on Aug.2023 due to delayed student onboarding during the pandemic that has arisen during the course of the project. As a result, additional time is required to fully accomplish the research goals and ensure the project's success. What opportunities for training and professional development has the project provided?The student meets weekly with the PI to update the research progress and issues encountered during the experiment. The PI helped provide timely feedback to ensure the progress of the project. The student has also been offered the opportunity to learn new instrumentations, including Thewas trained on how to use the particle size analyzer to determine the particle sizes of nanomaterials, SEM/EDX analysis of samples for surface analysis, GCMS analysis on bio-oils to determine their chemical composition. The student was offered opportunities in other collaborative work with one publications in 2023, one in 2024 The student presented in the SWST international convention to present his research findings both orally and in poster format, networking with other professionals in the filed and learn the newest research in the wood science field in general. provided peer-mentoring opportunities to help mentor an undergraduate student in learning how to conduct research in the laboratory and the research was published in a prestigious journal (Alorbu, C., Carey, J., McDonald, A.G. and Cai, L., 2023. Antifungal properties of lauric arginate (LAE) treated wood. Holzforschung.) How have the results been disseminated to communities of interest? The preliminary findings from this research have also been incorporated into the three courses: FSP 450/550 Biomaterial Deterioration and Protection, FSP 201 Forest and Sustainable Products for a green planet & ENVS 300 (s) Environmental Sci Seminar at the University of Idaho, to inform students about the newest research going on in the field of wood protection. The student was offered an opportunity to present his work both orally and in poster) about the ZnO-EG work at the Society of Wood Science and Technology conference in Asheville, North Carolina, June 25 -30, 2023. This conference had attracted over 200 attendees. What do you plan to do during the next reporting period to accomplish the goals?The following are the next experimental planned activities that will be conducted on the various projects. Part 1. ZnO-EG cement-treated wood Present data on long duration (6 weeks) accelerated weathering test on ZnO-EG treated wood Part 2. Replacing EG with wood pyrolysis oil and Clove oil as cheaper and more economical options for ZnO-based cement complex for wood protection Characterization of ZnO-CO and ZnO-PO treated wood (FTIR, TGA, etc.) Scaled-up fungal decay test on ZnO-CO and ZnO-PO treated wood Accelerated weathering test on ZnO-CO and ZnO-PO treated wood Hydrophobicity test on ZnO-CO and ZnO-PO treated wood Part 3. In-situ growth of nano ZnO in wood for the formation ZnO based cement complexes with PO and CO. Further Characterization of in situ growth of ZnO in wood (FTIR, TGA, etc.) Leaching test on situ growth of ZnO in wood Feasibility of reacting in situ ZnO treated wood with EG, PO, and CO and performing fungal decay test on ZnO-CO and ZnO-PO treated wood Accelerated weathering test in situ grown ZnO treated wood

Impacts
What was accomplished under these goals? The overarching goal of this project is to develop an environmentally friendly approach for wood protection using model chemicals, plant extracts containing phenolics and biologically active compounds,e.g. eugenol and nanoparticles, e.g., ZnO, both of which have their unique wood-protecting potency but also their weaknesses. The combination is hypothesized to be superior and provide synergistic protection efficacy for wood products. As such, thefirst partof the research is to demonstrate the feasibility of using ZnO-EG cement for improved wood protection, which was confirmed in our last year's progress report. The remaining experiment has been completed as scheduled, which includes the termicidal test, fire resistance test, accelerated weathering test, and hydrophobicity test on ZnO-EG treated samples. It was found that ZnO-EG treatment significantly prevents the termites' attack, does not make the wood more flammable and result in more char formation and residuals. Despite more color changes in ZnO-EG treated wood, the samples are more dimensional stable after two-weeks of artificial weathering process as compared to the untreated control. Moreover, the ZnO-EG treated wood becomes more hydrophobic with contact angles of nearly 90 degrees than those of the control at 20 degrees after 60 seconds of water sitting on the top of the wood samples. With promising data for the first part of the project, we proposed replacing eugenol with more cost-effective phenolic compounds, i.e., clove oils and pyrolysis oils. The main oil constituents of clove oils are eugenol (70-95 %), eugenol acetate (up to 20 %) and β-caryophyllene (12-17 %) while the main compositions in pyrolysis oils are phenolics. As of July 2024, the prices for eugenol, clove oil, and pyrolysis oil vary significantly due to differences in their production processes and applications. Based on global infor research https://www.globalinforesearch.com/reports/1837485/eugenol, the price of eugenol ranges from $35 to $45 per kilogram. Clove oil is priced between $20 and $30 per kilogram. Pyrolysis oil, derived from biomass, is less expensive, typically around $0.60 to $1 per liter, depending on the feedstock and processing technology used. The price disparities reflect the differences in their sources, extraction methods, and market demand?. Similar to what have been done in the first part of the project, the wood samples were treated with either clove oils or pyrolysis oils and then commercial nanoZnO. The samples were exposed to leaching test and the mass gain before and after leaching tests were collected. The samples were exposed to two brown rots (G.t. and R.p,) and two white rots (T.v. and I.l.), the results from the decay test showed that 5% and 10% Pyrolysis Oil (PO)-contained ZnO-PO cement-treated wood recorded mass loss < 5% regardless of leaching and fungal type. Replacing eugenol with clove oil in the ZnO based cement also provides similar results to ZnO-EG treatment. Therefore, clove oils and pyrolysis oils could be an feasible cost-effective alternative to EG in the formation of ZnO-based cement complexes in wood as environmentally sustainable wood preservatives. More research on other properties, such as weathering, fire etc. will be shared in the next annual report. The third part of this project is to directly grow nano ZnO in wood from precursor solutions of Zinc nitrate hexahydrate (Zn(NO3)·6H2O) and Sodium hydroxide (NaOH) following procedures described by Dong et al. (2017). This will serve as a cheaper and cost-effective option to the commercial water-dispersed nano ZnO selling on the market. The Zn(NO3)·6H2O and the NaOH were purchased from reputable for the preliminary study. First, 1M Zn(NO3)·6H2O solution was prepared by dissolving the solutes in DI water. Wood samples were conditioned at 60 ?C until a consistent weight was attained were submerged in Zn(NO3) solution and subjected to vacuum impregnation for 1h. After impregnation, the excessive solution on the wood surface was washed with DI water and rapidly immersed in the NaOH solution (0.4 mol/L) for 48 h at room temperature. Next, wood samples were washed with deionized water until they reached a neutral pH value. Finally, the samples were conditioned at 60 °C for 48 h to obtain ZnO-treated wood materials. To confirm the formation of ZnO in wood, wood sections were cut from the ZnO-treated wood samples using a microtome and samples were subjected to SEM/EDX analysis. The SEM images show the deposits of particulate in the cells of the treated wood compared to untreated control wood EDX analysis of the SEM images confirms that the deposits in the wood cells as ZnO nanoparticles with the associated peaks. Based on the preliminary data from the study, we can confirm this approach of in situ growth of ZnO in wood is feasible to explore further and hence more details of this research will be presented in the next annual report.

Publications

  • Type: Journal Articles Status: Published Year Published: 2023 Citation: Alorbu C, Carey J, McDonald AG, Cai L. Antifungal properties of lauric arginate (LAE) treated wood. Holzforschung. 2023 Aug 28;77(8):640-7.
  • Type: Conference Papers and Presentations Status: Published Year Published: 2023 Citation: Wood protection properties of Zinc Oxide-based Cement complex from Clove oil and wood pyrolysis oil; Presentation (both Oral and Poster) of ZnO-EG work at the Society of Wood Science and Technology conference in Asheville, North Carolina, June 25 -30, 2023


Progress 05/01/22 to 04/30/23

Outputs
Target Audience:One Ph.D. student from under representative minority group Students (8) who were taking FSP 450/550 Biomaterial Deterioration and Protection course at the University of Idaho: one undergraduate student and seven graduate students (two female + four Black or African Americans) High school students and community visitors from northern Idaho Changes/Problems:A no-cost extension of 1 year to 2025-04-30 for this USDA NIFA grant has been requestedThis extension will provide sufficient time for the successful completion of the project objectives. Student onboarding was during the pandemic. As a result, additional time is required to fully accomplish the research goals,ensure the project's successandproduce high-quality results that align with the objectives outlined in the grant proposal. Moreover, I have reassessed the budget for the remaining period of the project and can confirm that no additional funding is necessary to achieve the proposed objectives. We will utilize the remaining funds judiciously to support the completion of research activities and dissemination efforts within the extended timeframe. I understand the importance of adhering to grant deadlines and guidelines, and I assure you that I will make every effort to expedite the completion of the project within the requested extension period. What opportunities for training and professional development has the project provided?A Ph.D. student is hired and trained in this project as initially proposed. The student meets weekly with the PI to update the research progress and issues encountered during the experiment. The PI helped provide timely feedback to ensure the progress of the project. The student has also been offered the opportunity to learn new instrumentations, including 1) learning how to conduct CT scans of wood and wood products and how to process the data using different types of software; 2) Attending seminars and learning how to use the Xenon arc artificial weathering machine to conduct weathering tests on samples; 3) Professional training on how to use the Limited oxygen index instrument to determine how minimum amount of oxygen needed to sustain the flaming of the treated samples. In addition, the student 1)attended the Society of Wood Science and Technology (SWST), 2023 convention in Asheville, North Carolina where he presented our work as a speaker and participated in the poster competition to build public speaking skills and confidence; 2) attended seminars on how to write scientific articles and publications 3) provided peer-mentoring opportunities to help mentor an undergraduate student in learning how to conduct research in the laboratory and the research was published in a prestigious journal (Alorbu, C., Carey, J., McDonald, A.G. and Cai, L., 2023. Antifungal properties of lauric arginate (LAE) treated wood. Holzforschung, (0).) How have the results been disseminated to communities of interest?The preliminary findings from this research have also been incorporated into the FSP 450/550 Biomaterial Deterioration and Protection course to inform students about the newest research going on in the field of wood protection. The student was offered an opportunity to participate in 2023 Earth Day events to promote the use of wood products and had attracted over 300 students (high school and college students) stopped by the booster. Around 20 students expressed interest in a lab tour with Forest and Sustainable products program and the PI is currently coordinating the process. What do you plan to do during the next reporting period to accomplish the goals?Our preliminary trials have suggested that improved durability of ZnO-EG treated wood and we have conducted a larger scale experiment and would like to explore the muti-functionality of ZnO-EG treated wood through the testing below: Termiticidal properties of ZnO-EG treated wood. Artificial Weathering test on ZnO-EG treated wood. Fire Resistance of ZnO-EG treated wood (including the Limited Oxygen Index (LOI) & Mass loss cone test) Hydrophobicity test on ZnO-EG treated wood (contact angle test) Mechanical bending test of ZnO-EG treated wood. Other characterization methods will be explored to determine the presence and the formation of ZnO-EG cement in wood. We are also planning to collaborate with an expert in life cycle analysis to conduct a preliminary experiment on how the environmental impact of this new treatment differs from the traditional version. Finally, this study has opened a great opportunity to explore cheaper substitutes for eugenol or nano-ZnO, which we will work on in the next report period.

Impacts
What was accomplished under these goals? We have successfully completed the majority parts of the specific objectives (1) to (4) listed above. For specific objective (1) we have prepared sapwoods of southern yellow pine (softwood) and poplar (hardwood) according to the procedures of the American Wood Protection Association (AWPA) E-10 standards(AWPA, 2016), oven-dried, and weighed the samples. Based on our preliminary trial, we have finalized the treating concentrations to 1, 2.5, and 5% for both Zinc oxide (ZnO) and ZnO-EG. DI water and Eugenol (EG) treated samples were used as controls. A two-step vacuum impregnation method was employed to ensure the in-situ formation of ZnO-EG in wood by first impregnating wood samples with nano ZnO suspension and subsequently with EG solution. Objectives (2) study the penetrability of ZnO-EG in wood structure & (3) test the resistance of ZnO-EG to leaching due to extensive water leaching conditions. Upon treatment and leaching test, we measured the mass gain before and after leaching test. It was found that Retention & Mass gain generally increases with increasing treatment level, ranging from 2% to 12%. Further computerized tomography (CT) scan of ZnO-EG treated wood samples show chemical deposits in vessels but absent in controls. Also, ZnO-EG samples shows higher intensity of color change under CT scan as compared to EG and ZnO treated wood, indicating the penetration of ZnO-EG in wood structures. In addition, we also conducted FTIR and TGA analysis of the treated wood samples. Objective (4) examine the resistance of ZnO-EG treated wood against brown-rot and white-rot fungi. Our ZnO-EG treated wood samples and their counterparts were exposed to brown rot fungi, Gloeophyllum trabeum (G.t.) and Rhodonia placenta (R.p.) and two white-rot fungi, Trametes versicolor (T.v.) and Irpex lacteus (I.l.) in a soil-block test. We have found that 1) DI and EG samples recorded high mass loss > 25% for all fungi; 2) fungus R.p. appears resistant to ZnO but 5% ZnO-EG samples recorded mass loss < 3%. Similarly, when fungi G.t., T.v., & I.l. exposed to 5% ZnO-EG treated samples regardless of leaching have mass loss < 3%, indicating ZnO-EG treated wood has improved antifungal Properties.

Publications


    Progress 05/01/21 to 04/30/22

    Outputs
    Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?The PI meets with the student weekly to discuss the overall objective of this project, provided help in preliminary experiment design, preparation of fungal cultures and standard soil block test etc. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?if we are obtaining satisfactory results (with mass loss due to decay of all the four fungi less than 10%) from the preliminary testing, we will move to full-scale durability testing with different treating levels. In addition to using commercially available nano-ZnO for the treatment, we are planning to grow nano-ZnO in wood by in situ reaction of ZnSO4 and NaOH, before eugenol treatment.

    Impacts
    What was accomplished under these goals? Briefly, the wood samples from southern pined yellow poplar were first treated with various concentrations of commercial nano zinc oxide solutions (1% to 4%, 30-40 nm), followed by eugenol treatment. These samples were further subjected to a 14-day water leaching test following AWPA E11 standard. Our preliminary results found that over 60-100% of ZnO-EG was retained even under the harsh conditions (the mass gain after leaching was 12-95% ). We are planning to test the antifungal properties of the leached samples by exposing them to two brown rot and two white rot next month.

    Publications