Source: NORTH DAKOTA STATE UNIV submitted to NRP
NOVEL NANOCELLULOSE BASED FIRE RETARDANT FOR POLYMER COMPOSITES
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
COMPLETE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1013020
Grant No.
2017-67022-26609
Cumulative Award Amt.
$149,000.00
Proposal No.
2016-08777
Multistate No.
(N/A)
Project Start Date
Jun 15, 2017
Project End Date
Jun 5, 2020
Grant Year
2017
Program Code
[A1511]- Agriculture Systems and Technology: Nanotechnology for Agricultural and Food Systems
Recipient Organization
NORTH DAKOTA STATE UNIV
1310 BOLLEY DR
FARGO,ND 58105-5750
Performing Department
Mechanical Engineering
Non Technical Summary
Synthetic polymers are quite vulnerable to fire.There are 2.4 million reported fires, resulting in 7.8 billion dollars of direct property loss, an estimated 30 billion dollars of indirect loss, 29,000 civilian injuries, 101,000 firefighter injuries and 6000 civilian fatalities annually in the U.S. There is an urgent need for a safe, potent, and reliable fire retardant (FR) system that can be used in commodity polymers to reduce their flammability and protect lives and properties. The goal of this project is to develop a novel, safe and biobased FR system using agricultural and woody biomass. The project is divided into three major tasks. The first is tomanufacture zinc oxide (ZnO) coated cellulose nanoparticles and evaluate their morphological, chemical, structural and thermal characteristics. The second task will be to design and manufacture polymer composoites containing nano sizedzinc oxide and cellulose crystals. Finally the third task will be to test the fire retardancy and mechanical properties of the composites. Webelieve that presence of zinc oxide and cellulose nanocrystals in polymers will limit the oxygen supply by charring, shieldingthe surface andcellulose nanocrystals will makecomposites strong. The outcome of this project will help in developing a safe, reliable and biobased fire retardant for consumer goods, automotive, building products and will help in saving human lives and property damage due to fire.
Animal Health Component
40%
Research Effort Categories
Basic
30%
Applied
40%
Developmental
30%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
51106502020100%
Knowledge Area
511 - New and Improved Non-Food Products and Processes;

Subject Of Investigation
0650 - Wood and wood products;

Field Of Science
2020 - Engineering;
Goals / Objectives
The goal of this work is to evaluate a novel multifunctional cellulose nanocrystal (CNC) based fire retardant system (FR) for use in polymers. The CNCs will be functionalized by coating with nano-sized zinc oxide (ZnO) and the CNC-ZnO complex will be incorporated into the petroleum based polymer. The resultant polymer composites are expected to show improved fire resistance and mechanical properties due to charring and shielding or insulating of surface due to condensed and gaseous phase reactions initiated by CNC-ZnO complex and reinforcement by CNC respectively. CNC-ZnO complex is expected to improve UV resistance and impart antibacterial properties in composites. The project will explore the potential of a multifunctional cellulose nanocrystals (CNC) based FR system through following objectives:1. Synthesize zinc oxide (ZnO) coated cellulose nanoparticles and evaluate their morphological, chemical, structural and thermal characteristics.2. Design and manufacture polymer composites with functionalized ZnO-CNC complexes.3. Evaluate fire retardancy and mechanical properties of composites.
Project Methods
In this work we will exploit attributes of a hybrid inorganic-organic nanocomposite material for improving fire resistance and mechanical properties of polymers. Task 1: Synthesis of zinc oxide coated CNCs The chemical modification during synthesis aims to increase the apolar characteristics of ZnO (20-80 nm) so as to develop a better compatibility with hydrophobic matrices. The nucleation and growth of discrete ZnO particles on the surface will modify CNC to metal oxide CNC complexes. Based on previous studies three different ZnO-CNC complexes with three ZnO concentrations coated CNCs (3%, 5% and 8%) will be synthesizedby varying the ZnO density on the cellulose chains.Task 2: Characterization of ZnO Coated Cellulose NanocrystalsCNC with and without modification will be characterized to determine the concentration and distribution of ZnO inorganic particles on the cellulose. The bulk concentration of the ZnO nanoparticles, on the CNCs will be measured using inductively coupled plasma (ICP) analysis and FT-IR. Electron microscopy will be used to characterize the morphology of the CNCs and to determine if the surface modifications affect the size or morphology of the CNCs. A transmission electron microscope (TEM) equipped with energy-dispersive X-ray spectroscopy (EDX) and Atomic force microscopy (AFM) will be used to image the nanocrystals and to determine the distribution of metal oxide nanoparticles on the CNCs. Thermogravimetric analysis (TGA) will be employed to determine the thermal stability and degradation of the modified CNCs and final composites. After the initial characterization, four most promising formulations will be selected (two from each treatment) for the next objectives.Objective 2. To design and manufacture polymer composites coated with functionalized CNCs.High density polyethylene will serve as the matrix resin to manufacture composite samples. Four ZnO-CNC formulations selected in obj. 1 will be used to make HDPE masterbatches with 10% ZnO-CNC, 90% powdered HDPE. Freeze dried ZnO-CNC will be melt blended with resin using high intensity mixture. Each masterbatch will be further used at three levels (10%, 20% & 30%)to manufacture 12 test planks representing 1 to 3 wt% ZnO-CNC concentrations. Design of experiment will include four types of ZnO-CNC complexes at three levels and control (no ZnO-CNC) with 3 replications. For comparison a commercial fire retardant (Ammonium Phosphate, Exolit AP 422, Clariant) will be used. Co-rotating twin screw extruder with a combination of mixing elements will be used to ensure high shear melt blending and uniform dispersion of functionalized CNC in the polymer matrix. Uniformity of ZnO-CNC in extruded polymer samples will evaluated by TGA and TEM. The processing conditions and rheological properties will be recorded to understand the impact of CNC on resin. The extruded material will be injection molded into dog bones and sheets as per ASTM/UL specifications for mechanical and fire testing.Objective 3. Evaluate fire retardancy and mechanical properties of composites.Fire resistance characteristics of the polymer composites will be evaluated using, TGA, cone calorimetry and mass loss calorimetry at FPL. Samples will be tested following ASTM E84, ASTM E1354, and ASTM E119 that gives information on ignition time, heat release rate, and mass loss rate. Sample size will be 100mm x 100mm and 12 mm thickness of the board for fire tests. Mechanical property characterization will be conducted on conditioned samples according to the procedures outlined in ASTM standards D638, D790, and D256 respectively.

Progress 06/15/17 to 06/14/20

Outputs
Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported 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? Nothing Reported

Impacts
What was accomplished under these goals? PD has changed institutions and request to transfer the grant to new institution was initiated in 8/2019, so no work has occurred in this interim period waiting for approval to terminate at NDSU and initiate at MSU.

Publications


    Progress 06/15/17 to 06/05/20

    Outputs
    Target Audience: Nothing Reported Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided? Nothing Reported 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? Nothing Reported

    Impacts
    What was accomplished under these goals? PD has changed institutions and request to transfer the grant to new institution was initiated in 8/2019, so no work has occurred in this interim period waiting for approval to terminate at NDSU and initiate at MSU.

    Publications


      Progress 06/15/18 to 06/14/19

      Outputs
      Target Audience:Target Audience: Scientific Community - Researchers at privtate and public universities Participants from Industry - Focused on Nanotechnology for agricutlure and food stystems Students - Enrolled at institutions of higher learning Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities - The graduate student was trained on operating several material characaterization tools such as: Dynamic mechanical analyzer, Differential scanning calorimetry, FT-IR, D Universal tester etc. The students learned how to operate an extruder and injection molding machine. Professional Development - The PI attended a conference - Nanoscale Science and Engineering for Agriculture and Food Systems organized by Gordon Research Conference Dates: June 03, 2018 - June 08, 2018 Location: Mount Holyoke College in South Hadley, MA United States The conference helped PI to connect and establish links with other researches working with nano materials. This opportunity may help PI to collaborate with international researchers and develop future research proposals. 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?In the next six months the research will focus on completing the material characterization studies and manufacturing samples for testing and evaluation. The objective 2 - Design and manufacture polymer composites with functinailized CNC-ZnO complexes will be completed. In additon three commerically availalbe CNC will be characterized for their physical and thermal properties. If the project progresses as planned the fire test samples will be shipped to U.S. Forest Products Lab in Madison, WI for fire testing by end of 2018.

      Impacts
      What was accomplished under these goals? The primary impact of this research will be felt through the reduction in the loss of human lives and properties due to fires. The research will lead to the develpment of a safe, effective, reliable, and biobased fire retardants (FR) system for use in polymer/plastic products. The new biobased (functionailized nano cellulose) fire retardant system is going to reduce flame spread, smoke generation and heat geneartion during the fires. It is expected that a very small amount of this biobased FR (1 to 5%) will help in improving the fire resistance and strenght of plastic materials during extreme heat and fire. The new FR will help the plastic product manufactuerers to replace currently used toxic fire retardants. It will also help the U.S. farmers and tree growers through value addtion of cellulose a major component of trees. In the past 11 months the research team has focused on the objective 1 - Synthesis of nano zinc oxide (ZnO) coated cellulose nanocrystals (CNC) and evaluation of their morphological, chemical and thermal characeristics. The team evaluated several surface modification treatements for CNCs so they can be effectively coated with nano zinc oxide and uniformly dispersed in the polymeric matrix. The team was able to identify a suitable surface treatment method for CNC and the processing conditions requried to process polymer composites containing CNC-ZnO. Currently microscopy studies are underway to study the morphology of CNC-ZnO particles and to identify the best formuation/s for manufacturing test samples for fire testing. A few challenges encountered included agglomeration of CNC in polymer matrix as well as thermal degradation of CNC during processing. Therefore, we are going to evaluate the physical and thermal properties of three other commercially available CNCs in the market.

      Publications


        Progress 06/15/17 to 06/14/18

        Outputs
        Target Audience:Target Audience: Scientific Community - Researchers at privtate and public universities Participants from Industry - Focused on Nanotechnology for agricutlure and food stystems Students - Enrolled at institutions of higher learning Efforts: Presentation and technical talks at the professional conferences Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference Forest Products Society Annual Meeting Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?Training activities - The graduate student was trained on operatingseveralmaterial characaterization tools such as: Dynamic mechanical analyzer, Differential scanning calorimetry, FT-IR, D Universal tester etc. The students learned how to operate an extruder and injection molding machine. Professional Development - The PIattended a conference - Nanoscale Science and Engineering for Agriculture and Food Systems organized by Gordon Research Conference Dates: June 03, 2018 - June 08, 2018 Location: Mount Holyoke College in South Hadley, MA United States The conference helped PI to connect and establish linkswith other researches working with nano materials. This opportunity may help PI to collaborate with international researchersand develop future research proposals. 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?In the next six months theresearch will focus on completing the material characterization studies and manufacturingsamples for testing and evaluation.The objective 2 - Design and manufacture polymer composites with functinailized CNC-ZnO complexes will be completed. In additon three commerically availalbe CNC will be characterized for their physical and thermal properties. Ifthe project progressesas planned the fire test samples will be shipped to U.S. Forest Products Lab in Madison, WI for fire testing by end of 2018.

        Impacts
        What was accomplished under these goals? The primaryimpact of this research will be felt through thereduction in the loss of human lives and properties due to fires. The research will lead to the develpment of a safe, effective,reliable,and biobased fire retardants (FR) system for use in polymer/plastic products. The newbiobased (functionailized nano cellulose)fire retardant system is going to reduce flame spread, smoke generation and heat geneartion during the fires. It is expected that a very small amount of this biobased FR (1 to 5%) will help in improving the fire resistance and strenght of plastic materials during extreme heat and fire. The new FR will help the plastic product manufactuerers to replace currently used toxic fire retardants. It will also help the U.S.farmers and tree growers through value addtion of cellulose a major component of trees. In the past 11 months the research team has focused on the objective 1 - Synthesis of nano zinc oxide (ZnO) coated cellulose nanocrystals (CNC) and evaluation of their morphological, chemical and thermal characeristics. The team evaluated several surface modification treatementsfor CNCs so they can be effectively coated with nano zinc oxide anduniformly dispersed in the polymeric matrix. The team was able to identify a suitable surface treatment method for CNC and the processing conditions requried to process polymer composites containing CNC-ZnO. Currentlymicroscopy studies are underway to study the morphology of CNC-ZnO particles and toidentify the best formuation/s for manufacturing test samples for fire testing. A fewchallenges encountered included agglomeration of CNC in polymer matrix as well as thermal degradation of CNC during processing. Therefore, we are going to evaluatethe physical and thermal properties of three other commercially available CNCsin the market.

        Publications

        • Type: Conference Papers and Presentations Status: Accepted Year Published: 2018 Citation: Novel Nanocellulose Based Fire Retardant for Polymer Composites Poster presentation at - Nanoscale Science and Engineering for Agriculture and Food Systems Gordon Research Conference, S. Hadley, MA June 03-08, 2018