John R. Shields

Flame retardant mechanism of silica gel/silica

Various types of silica, silica gel, fumed silicas and fused silica were added to polypropylene and polyethylene oxide to determine their flame retardant effectiveness and mechanisms. Polypropylene was chosen as a non-char-forming thermoplastic and polyethylene oxide was chosen as a polar char-forming (slight) thermoplastic. Flammability properties were measured in the cone calorimeter and the mass loss rate was measured in our radiative gasification device in nitrogen to exclude any gas phase oxidation reactions. The addition of low density, large surface area silicas, such as fumed silicas and silica gel to polypropylene and polyethylene oxide significantly reduced the heat release rate and mass loss rate. However, the addition of fused silica did not reduce the flammability properties as much as other silicas. The mechanism of reduction in flammability properties is based on the physical processes in the condensed phase instead of chemical reactions. The balance between the density and the surface area of the additive and polymer melt viscosity determines whether the additive accumulates near the sample surface or sinks through the polymer melt layer. Fumed silicas and silica gel used in this study accumulated near the surface to act as a thermal insulation layer and also to reduce the polymer concentration near the surface. However, fused silica used in this study mainly sank through the polymer melt layer and did not accumulate near the surface. The heat release and the mass loss rate of polypropylene decreased nearly proportionally with an increase in mass loading level of silica gel up to 20% mass fraction. Polyethylene oxide samples with fumed silicas and silica gel formed physically strong char/silica surface layers. This layer acted not only as thermal insulation to protect virgin polymer but also acted as a barrier against the migration of the thermal degradation products to the surface.

Ignition of mulch and grasses by firebrands in wildland–urban interface fires*

Firebrands or embers are produced as trees and structures burn in wildland–urban interface (WUI) fires. It is believed that firebrand showers created in WUI fires may ignite vegetation and mulch located near homes and structures. This, in turn, may lead to ignition of homes and structures due to burning vegetation and mulch. Understanding the ignition events that are due to firebrands is important to mitigate fire spread in communities. To assess the ignition propensity of such materials, simulated firebrands of uniform geometry, but in two different sizes, were allowed to impinge on fuel beds of shredded hardwood mulch, pine straw mulch, and cut grass. The moisture content of these materials was varied. Firebrands were suspended and ignited within the test cell of the Fire Emulator/Detector Evaluator (FE/DE) apparatus. The FE/DE was used to investigate the influence of an air flow on the ignition propensity of a fuel bed. Ignition regime maps were generated for each material tested as a function of impacting firebrand size, number of deposited firebrands, air flow, and material moisture content.

Controlling polyurethane foam flammability and mechanical behaviour by tailoring the composition of clay-based multilayer nanocoatings

This study is a thorough evaluation of clay-based Layer-by-Layer (LbL) coatings intended to reduce the flammability of polymeric materials. Through a systematic variation of a baseline coating recipe, an ideal combination of the coating attributes that provides a rapidly developing coating with an optimum balance of flammability, mechanical, and physical attributes on a complex 3D porous substrate, polyurethane foam (PUF) was identified. Using a unique trilayer (TL) assembly approach, the coating growth was significantly accelerated by the polymer (poly(acrylic acid) (PAA)/branched polyethylenimine (BPEI)) concentration in the formulation. However, to significantly reduce flammability without compromising other performance attributes, the concentration of the nanoparticle fire retardant (nanoFR, clay) suspension was critical. This study has resulted in the most significant reduction in PUF flammability using LbL technology without compromising any of the mechanical or physical attributes of the PUF. More specifically, a reduction in the peak heat release rate (pHRR) and average heat release rate (aHRR) of 33% and 78%, respectively, has been achieved. This reduction in flammability is at least two times more effective than commercial fire retardants and other LbL FR coatings for PUF. The insights gained through this research are expected to accelerate the development of other LbL coatings regardless of the intended application.

Synthesis and characterization of isosorbide-based polyphosphonates as biobased flame-retardants

A new isosorbide-based polyphosphate was synthesized and applied as a flame-retardant for polylactic acid (PLA). The storage modulus and glass transition temperature of PLA/polyphosphonate blends was unaffected by the inclusion of polyphosphonate, but moderate depressions of PLAs tensile strength (16%, 28%, and 45% reduction from PLA at a polyphosphonate mass percentage of 5%, 10%, and 15%, respectively) and strain-at-break (0%, 17%, and 30% reduction from PLA at a polyphosphonate mass percentage of 5%, 10%, and 15%, respectively) were observed. Modified UL-94 flammability testing indicated that isosorbide-based polyphosphonates are effective flame retardants for PLA and are able to self-extinguish flames in less than 2 s to achieve V2 and V0 ratings at polyphosphonate mass percentage of 5% and 15%, respectively. Fire test data indicates a gas phase mechanism that can quench the flame when no external radiant heat flux is present (e.g., in modified UL-94 testing) but does not affect the materials heat release rate in forced combustion (e.g., in cone calorimetry). Use of the biobased flame retardants described herein yields flame retardant PLA containing up to 97% by mass of bio-derived content.

Investigating the Vulnerabilities of Structures to Ignition From a Firebrand Attack

A unique experimental apparatus, known as the Firebrand Generator, was used to generate a controlled and repeatable size and mass distribution of glowing firebrands. The size and mass distribution of firebrands produced from the generator was selected to be representative of firebrands produced from burning vegetation. The vulnerability of roofing materials to firebrand attack was ascertained using fluxes of firebrands produced using this device. The experiments were performed at the Fire Research Wind Tunnel Facility (FRWTF) at the Building Research Institute (BRI) in Tsukuba, Japan. A custom mounting assembly was constructed to support full scale sections of common roofing materials inside the FRWTF. The sections constructed for testing included full roofing assemblies (base layer, tar paper, and shingles) as well as only the base layer material, such as oriented strand board (OSB). The custom mounting assembly allowed for the construction of flat roofs as well as the construction of angled roofs (valleys). Results of this study are presented and discussed.

The effect of surface coatings on fire growth over composite materials in a corner configuration

Structural composites are vulnerable to fire in two respects: (1) their resin content may ignite and enable the spread of flames over the surface of the structure; (2) the resin may degrade from the heat of a localized fire exposure thus weakening the composite structure. The present study focuses mainly on the first issue, in particular, on the ability of various commercial coatings to prevent flame spread. The second issue is examined briefly by applying thermocouples to the back surface of test specimens. Four commercial coatings have been tested over an unretarded vinyl ester/glass composite. In addition an uncoated phenolic/glass composite and a polyester/glass composite coated with a fire retarded resin were tested. In all cases the configuration was a 3.3 m high corner with a 53 cm square propane gas burner at its base, operated at 250 kW as the fire exposure. The results show that, with the proper choice of coating and coating thickness, fire growth can be suppressed quite effectively. Two of the coatings, applied at a substantial thickness, were reasonably effective at slowing the penetration of heat to the back of the composite panels. The other coatings, much thinner in application, were notably less effective at slowing heat penetration.

Effect of ignition conditions on upward flame spread on a composite material in a corner configuration

This paper focuses on the issue of fire growth on composite materials beyond the region immediately subjected to an ignition source. Suppression of this growth is one of the key issues in realizing the safe usage of composite structural materials. A vinyl ester/glass composite was tested in the form of a 90° corner configuration with an inert ceiling segment 2.44 m above the top of the fire source. The igniter was a square propane burner at the base of the corner, either 23 or 38 cm in width, with power output varied from 30 to 150 kW. Upward flame spread rate and heat release rate were measured mainly for a brominated vinyl ester resin but limited results were also obtained for a non-flame retarded vinyl ester and a similar composite coated with an intumescent paint. Rapid fire growth to the top of the sample was seen in replicate tests for the largest igniter power case; the intumescent coating successfully prevented fire growth for this case.

High Throughput Flammability Characterization Using Gradient Heat Flux Fields.

The quest for small-scale flammability tests useful for predicting large-scale fire test performance is an enduring undertaking. Often, this work is motivated by limited access to larger quantities of samples, in the case of materials development efforts, and by the slow turn-around and high cost of large scale flammability testing. Use of Cone calorimeter data such as heat release rate (HRR) and ignition data has been coupled with various models to attempt to predict the performance of materials in medium and large scale fire tests. In some instances this has been successful; however, the extensive amount of data that needs to be acquired has motivated the High Throughput (HT) Flammability program at the National Institute of Standards and Technology (NIST) to develop flammability characterization methods which significantly increase the rate of data generation. The goal is to keep pace with our sample preparation rate, which is a significant challenge since our capability to produce samples, either extruded rod, or gradient coatings, has developed to a rate of one sample per minute! The efforts described here are those specifically focused at developing HT flammability analysis methods. The method of evaluating the flammability of a sample at a variety of fluxes simultaneously involves use of a radiant panel to create a gradient heat flux field. Samples are ignited in the high flux region and burned until they self-extinguish. The local flux at this position is termed the minimum flux for flame spread (MFFS). The same general technique has also been accomplished on a smaller scale using the Cone calorimeter. Here MFFS and HRR can be measured concurrently.

Assessing the Flammability of Composite Materials

COMPOSITE MATERIALS OFFER the potential for substantial weight savings in the structure of both surface ships and submarines. However, the organic nature of the binder resins in these materials implies that one would be replacing non-flammable materials (aluminum, steel) with materials that could possibly contribute to a fire. This points to a critical need for methods which allow reliable prediction of the extent of fire involvement which a given material may exhibit in a particular application. There are numerous aspects of this which must ultimately be considered; these range from the strength of the composite under a fire heat load to potential toxicity and corrosivity of the fire

Development of High-Throughput Methods for Polymer Nanocomposite Research

This chapter will present an overview of the development of two high-throughput (HT) methods: (1) preparation of formulated polymer libraries using extrusion; (2) screening of flammability properties using flame- spread measurements.