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FLAME RETARDANT

Flame Retardants are additive or reactive chemical systems used to alter the ignition, flame spread, heat release, and in some cases smoke generation behavior of materials such as plastics, rubber, coatings, foams, textiles, cables, and composites. Flame Retardants is not the name of a single pure chemical substance; it is a broad family of products with different mechanisms. Therefore, a single CAS number, molecular formula, molecular weight, or standard dosage cannot be specified for all flame retardants.
Commercial products include aluminum trihydroxide (ATH), magnesium hydroxide (MDH), ammonium polyphosphate (APP), metal phosphinates, phosphate esters, melamine derivatives, expanding graphite, and certain brominated systems. These products can be added to the polymer by physical stirring or chemically bonded to the structure of the polymer in some reactive systems. The amount of additive in the recipe; It should be evaluated together with the polymer type, filler ratio, thickness of the part, target test standard and process temperature.
The overall goal of flame retardant additives is not to make the material "fireproof", but to delay the onset or development of fire under certain conditions, to reduce the spread of flame, or to support the formation of a protective charred layer. Just because a product achieves UL 94 V-0 does not mean that it is safe in all fire scenarios. Smoke content, toxic gas generation, heat dissipation, dripping, and full system behavior should be measured separately.
This dossier discusses the main halogen-free systems and their alternatives in detail. Formulation samples are initial recipes prepared for laboratory screening purposes only; they are not a substitute for manufacturer approval, performance guarantee, or fire safety certification.

WHAT IS FLAME RETARDANT?

Flame Retardant is an additive or combination of additives that intervene in the combustion chain of a material by physical or chemical means. For combustion, heat, oxygen, and fuel must interact. Flame retardants target one or more of these interactions: absorb heat, form a barrier on the surface, change breakdown products, or suppress radical reactions in the gas phase.
Additive flame retardants are added to the polymer in the existing production process. Reactive flame retardants are chemically incorporated into the structure of some resin, polymerization or curing systems. There are significant differences between these two approaches in terms of migration, long-term stability, cost, ease of production and material properties.
ATH and MDH are mineral hydroxides that release water under heat. APP and other phosphorus products can promote carbonization, especially in the condensed phase. Melamine derivatives can synergize with nitrogen source, gas formation, or phosphorus systems. Expanding graphite forms a barrier layer with physical volume increase. Some halogen-containing additives can act on gas-phase radical chemistry, but environmental, health, and regulatory considerations vary by product.
Material class, target thickness, thermal processing conditions, mechanical property requirements, electrical properties, smoke toxicity and regulatory requirements of the target market are the initial parameters in the selection of flame retardants.

COMMON PRODUCT AND CHEMICAL NAMES

Flame Retardant

Fire Retardant

Halogen-Free Flame Retardant (HFFR)

Halogen-Free Flame Retardant

Ammonium Polyphosphate (APP) – Amonyum Polifosfat

Aluminium Trihydroxide / Aluminium Hydroxide (ATH) – Alüminyum Trihidroksit

Magnesium Hydroxide (MDH) – Magnezyum Hidroksit

Metal Phosphinate – Metal Fosfinat

Melamine Polyphosphate (MPP) – Melamin Polifosfat

Expandable Graphite – Genleşebilir Grafit

Phosphate Ester – Fosfat Esteri

Brominated Flame Retardant – Bromlu Alev Geciktirici

Intumescent Flame Retardant – Flame Retardant That Inflates and Forms a Barrier

CAS NO, EC / EINECS NO AND CHEMICAL IDENTIFICATION

Product group: Flame Retardant / Flame Retardant

Single CAS number: None

Single molecular formula: None

Single molecular weight: None

Physical form: Powder, granule, masterbatch, dispersion, or liquid; varies depending on the product type

Main function: Changing combustion and fire response

ATH: Al(OH)₃, CAS No 21645-51-2; molar mass approx. 78.00 g/mol.

MDH: Mg(OH)₂, CAS No 1309-42-8; molar mass approx. 58.32 g/mol.

APP: Ammonium polyphosphate, polymeric phosphate salt; common CAS No 68333-79-9. Due to the polymeric structure and chain length, it should not be reduced to the single definitive molecular weight.

Melamine: C₃H₆N₆, CAS No 108-78-1; molar mass about 126.12 g/mol.

The above example CAS numbers refer only to the chemicals mentioned; they do not cover all commercial products sold under the Flame Retardant name. SDS Part 3 and COA information should be checked separately for coated, surface-treated or blended products.

FLAME RETARDANT CHEMICAL STRUCTURE AND MOLECULAR PROPERTIES

Mineral-based flame retardants are crystalline inorganic compounds. The hydroxyl groups in the ATH and MDH structure can decompose at high temperature and release water. This endothermic process consumes heat from the environment. The solid metal oxide residue formed can also contribute to the barrier effect on the surface of the material.
APP is polymeric ammonium salt with phosphate units repeated in chains. When heated, the formation of phosphoric/polyphosphoric acid derivatives promotes the development of the charred phase as a result of reaction with the appropriate carbon source. In intumescent coatings, APP is usually considered as an acid source; pentaerythritol is a carbon source; and melamine is considered as a gas-forming component.
The behavior of phosphorus-based reactive additives depends on their functional groups. Phosphinate, phosphonate, and phosphate esters are not the same class. Some systems can affect the condensed phase, some affect the gas phase, and some affect both mechanisms. Therefore, flame retardant performance equivalence cannot be established by looking only at the total phosphorus percentage.
Expanding graphite can form a carbon barrier that thickens by the heat expansion of interlayer components. The particle size of the additive particle and the initial temperature of expansion are critical parameters according to the application. Compatibility with the polymeric matrix and homogeneous dispersion are important in all these approaches.

PHYSICAL AND CHEMICAL PROPERTIES OF FLAME RETARDANT

Appearance: ATH and MDH are usually white mineral powder; APP is usually white, free-flowing particle; expanding graphite is in the form of dark colored flakes/powder. There are also liquid phosphate esters and masterbatch forms. It is not correct to define different products by their common single density or melting point.
When heated, ATH releases water endothermically. The Huber Martinal product family states that ATH is used for many polymer compounds that require processing temperatures of about 210 °C or lower. This information does not mean that the exact decomposition start of each ATH grade is 210 °C.
MDH may be suitable for some systems that require a higher processing temperature compared to ATH; however, the actual degradation range depends on the particle structure and product grade. In APP products, the degree of polymerization, water solubility, particle dispersion, and surface coating are important. For example, Exolit AP 422 is defined as a low water soluble phase II ammonium polyphosphate.
In particular, the following data should be sought in the technical data sheet: active substance type and percentage; particle size distribution (D10/D50/D90); density and bulk density; specific surface area; moisture; water solubility; pH; thermal decomposition initiation; surface treatment; color; impurity profile and recommended process range.
A high percentage of mineral filler can increase viscosity, reduce elongation, and create an abrasive effect on the equipment. Fine particles create a higher interface area, but can make dispersion and dust control difficult. Therefore, not only flame test success, but also the mechanical and process properties of the final product must be monitored together.

HOW DOES FLAME RETARDANT WORK AT THE MOLECULAR LEVEL?

When the polymer is heated, softening and subsequent thermal degradation processes can occur. When the resulting volatile fuel components react with oxygen in the air, a flame is formed. Flame retardant additives can slow down the transport of heat to the polymer, alter the thermal degradation pathway, or limit fuel output by forming a protective solid layer on the surface.
In endothermic mineral systems, the release of water by ATH or MDH allows energy to be consumed during decomposition. The water vapor released can contribute to reducing the local density of flammable gases to a certain extent; residual mineral oxide partially limits heat and mass transport. Loss of mechanical properties is possible because significant fill ratios are often required for high efficiency.
In intumescent systems, the phosphorous component creates an acidic environment and promotes the charring of the carbon source. With the introduction of the gas-forming material, the foamed carbon layer thickens. This layer can delay the temperature rise of the substrate. The ratios of APP, pentaerythritol and melamine, the chemistry of the binder, the coating thickness and moisture resistance greatly change the result.
Some brominated additives can affect combustion reactions in the gas phase with appropriate synergists. However, halogenated or halogen-free labels alone are not a measure of smoke toxicity, health risk, or final fire performance. Each specific formulation, usage scenario, and regulatory requirement should be evaluated separately.

IN WHICH SECTORS IS FLAME RETARDANT USED?

Wire and cable sheaths; electrical-electronic enclosures; automotive interior trims; rail system components; building materials; wood fire protection coatings; steel carrier fire protection systems; composite panels; polyurethane foams; polyester and epoxy laminates; floor coverings; technical textiles; adhesives; mastics and thermoplastic injection parts are important application areas.
In the cable industry, halogen-free low-smoke compounds are often designed with mineral fillers and compatibilizing additives. For electronic parts, combustion tests such as UL 94 may be required with thin section thickness. In building coatings, the fire resistance period and class of the final product or building element come to the fore.
In transportation applications, not only flame spread but also parameters such as smoke intensity, smoke toxicity, and visibility under smoke can be critical. Therefore, each industry's evaluation standard should be selected based on its end-use scenario.

FLAME RETARDANT POLYMER, CABLE AND THERMOPLASTIC APPLICATIONS

For thermoplastics such as polyethylene and EVA, ATH or MDH-based filler systems can be used to improve flame behavior. When the total solid load of the formulation increases, processability becomes difficult; proper polymer grade, bonding and surface treatment strategy become important.
Phosphorus-nitrogen based tumescent systems can be evaluated in PP and some other polyolefins. Pure APP alone does not give the same result in every polyolefin; Clariant's technical descriptions emphasize appropriate synergist combinations and application-specific ready-made additive packages.
Chlorine in the structure of PVC itself affects combustion behavior; however, additional flame retardant or smoke suppressant package may be required due to the plasticizer ratio, smoke generation and final application objectives. Cable PVC and EVA/PE halogen-free cable compound should not be designed with the same recipe.
If a masterbatch is used, the concentration of active flame retardant must be taken into account. For example, using 20% of a masterbatch with 50% active filler provides only 10% active filler to the final recipe. It should be clearly written whether the recipe percentages are based on active base or commercial product.

FLAME RETARDANT INTUMESCENT FIRE PROTECTION COATINGS

Intumescent coatings are designed to expand in volume with heat to form a carbonaceous foam layer that delays heat transfer. The binder, acid source, carbon source, gas-forming component and auxiliary pigment/fillers must work together.
APP plays a fundamental role in many intumescent coatings as a source of phosphorus. Pentaerythritol or dipentaerythritol is the source of carbonization, and melamine is one of the components that support gas output. Titanium dioxide and some mineral fillers can affect the structure of the formed coal layer.
Just because a coating formulation yields 100% total does not mean it will provide fire resistance. Wet film thickness, dry film thickness, underlayment preparation, primer/topcoat compatibility, curing, moisture, and aging performance must be verified. Structural element assessments such as EN 13381 are not a substitute for UL 94 small sample tests.
Low water solubility APP grades can be preferred for water-based coatings. However, viscosity, pH, agglomeration, sedimentation and water resistance should be checked separately in long-term storage.

FLAME RETARDANT FOAM, TEXTILE AND COMPOSITE APPLICATIONS

The choice of flame retardant in polyurethane foam systems depends on the formation of rigid or flexible foam, polyol and isocyanate chemistry, catalyst package, and target density. Some APP grades can be used in specific foam systems; however, foam cell structure, reactivity, and mechanical strength must be tested.
In textile applications, finishing strength, wash strength, hand, color and possible migration are important quality parameters. Successful preparation of a water-based textile finish does not automatically verify the final fire class of the fabric.
Phosphorus additives, expanding graphite, or special resin components can be used in epoxy, polyester, and phenolic composites. The glass fiber ratio, resin-to-additive interface, degree of curing, and thickness of the test sample significantly influence the results.
In high-performance composites, heat dissipation rate, smoke and toxic gas composition and mechanical strength loss should be evaluated together. In vehicle and construction applications that require certification, only the manufacturer's brochure of a single additive is not sufficient.

IS FLAME RETARDANT USED IN FOOD, COSMETICS AND PHARMACEUTICAL APPLICATIONS?

Flame retardant chemicals are generally not standard ingredients that are directly added to food. Flame retardant packaging polymer and the substance added to food are completely different applications. If there will be food contact, the full commercial grade, migration of additives and relevant food contact legislation should be verified.
Cosmetic or pharmaceutical use cannot be generalized through the product name Flame Retardant. The presence of some mineral substances in related sectors for other purposes does not mean that the technical flame retardant grade of the same substance is of cosmetic or pharmaceutical quality.
All conformity certificates, including restricted substances, residual monomers, heavy metals, dust exposure and post-use waste management, should be checked for products that come into contact with the consumer for a long time.

FLAME RETARDANT INDUSTRIAL APPLICATIONS

Main technical objectives: To reduce the tendency to ignite; to delay flame spread; to limit heat dissipation; to form a char layer; to change molten drip behavior; to reduce smoke density in some systems; to ensure that electrical parts approach the target class in flame tests; to support fire performance in cables and composites.
Not all of these goals should be expected from the same contribution. For example, some systems may not adequately reduce smoke production while providing easy extinguishing. In assessing smoke toxicity under heat, the "halogen-free" declaration alone is not sufficient.
Distribution uniformity, extruder torque, filter pressure, material moisture, wear, color change and long-term thermal aging performance should be monitored at the production scale. The optimum system is the technical balance between fire testing and machinability/mechanical performance.

WHAT PROBLEMS CAN FLAME RETARDANT HELP SOLVE?

Polymer is easily ignited: A phosphorous, mineral, or synergistic additive package suitable for the polymer chemistry and target test can be evaluated.

High smoke is generated in the cable sheath: HFFR mineral systems can be examined according to the requirements of not only flammability but also smoke density and gas acidity.

Intumescent coating does not swell sufficiently: APP, carbon source, gas source, binder compatibility, and dry film thickness should be reviewed together.

Very brittle after thermoplastic filling: Particle distribution, surface treatment, polymer ratio, compatibilizer and total mineral load must be re-optimized.

Poor flame test in cured composite: Resin curing, fiber distribution and sample thickness should be checked as well as additive type and ratio.

Coating precipitation occurs: APP particle distribution, dispersant, consistency control, and storage stability must be tested.

Sample that passes the fire test fails in another thickness: It should be accepted that the test class may depend on the geometry and thickness; the target final thickness should be tested separately.

Smoke level high: Instead of upgrading the flame retardant, the choice of smoke suppressant, polymer, and the fire chemistry of the entire system should be re-evaluated.

THINGS TO CONSIDER WHEN USING FLAME RETARDANT

The product family and the exact commercial grade should be verified. CAS number and SDS composition should be examined. Particle size, surface treatment, moisture and processing temperature of minerals should be checked. For APP, the degree of polymerization, water solubility and thermal stability are important. In halogenated systems, REACH, RoHS and other target market constraints should be checked on the basis of the relevant substance.
In the formulation calculation, the mass percentage, phr (parts per 100 units of resin) and masterbatch active percentage should not be confused with each other. These are different calculation methods. For example, 40 phr additives do not always mean 40% additives in the final mixture.
High density in mineral additives can increase the final product weight. Fine powders can lead to workplace dust exposure. Insufficient ventilation and excessive process temperature during heat treatment can lead to polymer degradation. The current SDS and occupational safety procedures of the relevant grade should be taken as basis.
Before a laboratory recipe can be converted into a real product, fire performance, mechanical tests, aging, migration and end-use safety must be further verified.

CRITICAL PARAMETERS IN FORMULATION DESIGN FOR FLAME RETARDANT

In formulation development, the first decision is whether the performance objective is reaction to fire, smoke suppression, preservation of mechanical properties, or preservation of the structural element for a certain period of time. Clarifying the target facilitates the choice between mineral filler and phosphorus intumescent system. For example, acceptable elongation in cable sheath is critical, while in steel structure, the stability of the high-temperature coal layer may be more decisive for intumescent coating.
A decrease in particle size increases the surface area. This may provide an advantage in terms of dispersion and some interactions, but may be a disadvantage in terms of viscosity and dust formation. A low D50 value of an ATH product does not automatically mean that it will give better results in all mechanical and fire properties. Grain distribution, surface treatment and interfacial relationship with the matrix should be evaluated together.
Compatibilizers or surface treatment agents can alter the filler-polymer interaction. Maleic anhydride-infused polymers can be used in polyolefin systems. However, increasing their quantity alone does not solve all flexibility and fracture problems in high filler applications. The chemistry of the filler surface, the polymer molecular weight, and the shear profile of the process are also important.
The active solids ratio of the binder dispersion used in coating systems is very important. Two different acrylic dispersions of the same weight may not provide an equal amount of dry polymer. For this reason, dry matter calculations should be kept separately when starter recipes are given as 100% on a commercial product basis. It should be noted that part of the water phase will be removed by drying and the final dry film composition is not the same as the wet recipe.

FLAME RETARDANT CORROSION, ENVIRONMENTAL BEHAVIOR AND LONG-TERM STABILITY

The choice of flame retardant additive should consider long-term usage conditions as well as short-term performance seen during fire testing. Humidity, temperature change, UV exposure, washing, and mechanical fatigue can affect the distribution of some admixture systems on the surface or their bond with the matrix. Post-aging re-fire testing is important, especially for textiles and outdoor coatings.
In intumescent coatings, phosphate sources with high water solubility may cause dispersion or surface defects over long moisture contact. Opting for low water solubility APP grades can help mitigate this risk; however, it does not guarantee the water resistance of the completed paint system on its own. The hydrolytic stability of the binder, coating porosity, and top coat compatibility should also be evaluated.
In mineral-filled thermoplastics, microcrack formation under thermal cycles and bending can affect the electrical and mechanical performance of the material. In cable applications, water aging, deburring, and electrical properties must be monitored according to the conditions of end use.
The environmental impacts of flame retardants are different between families and between substances within the same family. The declaration of being halogen-free does not automatically prove that the product is easily biodegradable or ecotoxicologically risk-free. Similarly, for a brominated additive to be evaluated, its commercial identity and specific regulatory status must be known.
The additive composition present in waste electrical-electronic products, construction materials, or recycled polymers should be monitored. In recycling, the processing temperature, the thermal history of the old additive, and the presence of restricted substances may affect processing and sales suitability. The life cycle and waste management assessment of the final product should be part of the supplier documentation chain.

FLAME RETARDANT PARTICULATE ENGINEERING AND DISPERSION CONTROL

The relationship between the grain size distribution of the flame retardant particle and the polymer matrix is important not only for ease of production but also for final performance. The high surface area of fine ATH or MDH particles interfaces more within the polymer. However, it is possible for very fine powders to be prone to agglomeration and increase viscosity during mixing. Therefore, it is advantageous to request grain distribution values such as D10, D50, D90 and the measurement method in the purchase specification instead of single D50.
Surface-treated mineral fillers can alter the wetting behavior of the polymer. The choice of silanes, fatty acid derivatives, or other manufacturer-specific surface treatment packages depends on the polymer chemistry. The fact that an additive has been surface-treated does not guarantee better mechanical strength in every EVA or PE recipe. The optimum level of compatibilizer may be different between low-fill and high-filler recipes.
In thermoplastic compound production, gravimetric feed consistency, powder flowability, and effective mixing capacity of the extruder are important. High mineral loading can increase torque and melt pressure. Overheating the mixture at certain points can lead to unwanted polymer degradation or color aberration. Particle breakage, filter clogging, and uneven pellet quality should also be monitored.
Homogeneous distribution of APP, melamine and carbon source solid particles is essential in coating dispersions. If the amount of dispersant is insufficient, rapid settling may occur, and if it is too high, water resistance or foaming may be adversely affected. Paint viscosity needs to be checked not only at the end of production, but also after storage and remixing. Re-homogenization of the precipitated system by mixing does not mean that permanent stability has been confirmed.
In the initial trials, the raw material lot, mixing sequence, temperature, total mixing energy, time, filling date and pre-test waiting conditions of each sample should be recorded. Otherwise, it will be difficult to determine the cause of the performance difference as the process variables will change as the additive level is changed.

FLAME RETARDANT ECONOMIC AND TECHNICAL OPTIMIZATION

In the economic evaluation of flame retardant additives, one should not only compare the price per kilogram of raw materials. Mineral fillers can be provided at a low unit price, but high filler rates can increase the density of the material and the unit product weight. For example, in a cable sheath of the same size, an increase in density increases the kilograms consumed per length. Therefore, the actual cost should be calculated based on the additive consumption per product and the appropriate production rate.
The required dosage of phosphorus additives may be lower in some polymers than in mineral hydroxides; however, the product price, compatibility with the polymer, synergist used, and final fire performance are different. Low dosage alone does not mean a cheaper system. Successful fulfillment of the target fire test, the rejection rate of the final part, and the need for additional mechanical reinforcement should be included in the cost calculation.
In technical optimization, outputs to be evaluated separately should be determined: UL 94 or related combustion result, LOI, tensile strength, elongation at break, hardness, density, extrusion torque, flow rate, color, surface finish and cable electrical tests, if applicable. A recipe should not be considered successful if only one result improvement is achieved while other critical criteria go beyond the acceptance limit.
Cost analysis for intumescent coating should include the consumption of material that provides the target dry film thickness per square meter instead of kilograms of wet paint. With increasing amount of APP, viscosity, applicable coat thickness or tendency to crack due to drying may change. Higher dry matter or thicker coating does not provide a better fire resistance time in all conditions. The approved paint system and application conditions should be evaluated together.
When changing suppliers, it is not enough for two APP or ATH grades to be identical as a chemical family. Moisture, water solubility, grain size, surface treatment and particle morphology can change the process results. The new supplier product must first be compared on a laboratory and pilot scale; the acceptance decision must take into account not only the raw material certificate but also the final application test.

COMMON TECHNICAL ERRORS IN FLAME RETARDANT APPLICATIONS

The first mistake is to treat all flame retardant products as the same chemical. Flame Retardant is a general function description. Ammonium polyphosphate, aluminum hydroxide, expanding graphite, and phosphate esters have different processing, storage, and chemical interaction properties. Writing only flame retardant in the purchase order can result in incorrect chemical sourcing and costly manufacturing trials.
The second mistake is to mix the percentage of use with the phr value or masterbatch dosage. For example, adding 50 phr mineral additives to the resin means approximately 33.3% additives in the final product if the total mixture consists of only these two components. In addition, a 20% commercial additive added as a masterbatch provides only 10% actual active flame retardant if the active concentration of the masterbatch is 50%. The percentage method based on should be clearly written in the technical reports.
The third mistake is to generalize the class of the small test sample to all final products. UL 94 results depend on sample thickness and test setup. The geometry, other components and assembly of the end product can change the fire behavior. In particular, the fire resistance of structural elements and the fire behavior of wiring harnesses should be measured according to their appropriate standards.
The fourth mistake is to neglect machinability while increasing the solid additive ratio. Filler increase can affect melt viscosity, density, mechanical elongation, and surface finish. Performance gain should be considered in conjunction with acceptable production conditions.
The fifth mistake is to conclude a safe product based solely on a halogen-free or low smoke declaration. The gases, heat dissipation and smoke density produced during the fire depend on the actual material system and combustion conditions. The manufacturer or formulator must ensure that the entire product is evaluated with appropriate safety and performance tests.

INITIAL FORMULATION APPROACHES FOR FLAME RETARDANT

Eight separate starting recipes were given within the scope of the following two applications. All raw materials are indicated as a percentage by weight over the final mixture, and the total of each recipe is 100.00%. These are not recipes that have been verified for commercial production, product certification or regulatory compliance.
ATH and APP quantities refer to the percentage of active raw materials. If commercial products contain water or carriers, the ratios must be recalculated. The raw material grades and test conditions used in comparisons must be kept constant.

EXAMPLE 1: ATH LEVEL SCAN IN HFFR EVA/PE CABLE COMPOUND

Purpose: To compare the effect of ATH ratio on combustion behavior, mechanical property, and extrusion processability in halogen-free EVA/PE cable compound.

Starting components:

CONTROL A (wt%):

EVA copolymer: 54.00%
LLDPE: 45.00%
Aluminum trihydroxide (ATH): 0.00%
PE-g-MA compatibilizer: 0.50%
Antioxidant packet: 0.30%
Process slider: 0.20%
TOTAL: 100.00%

EXAMPLE B (wt%):

EVA copolymer: 39.00%
LLDPE: 30.00%
Aluminum trihydroxide (ATH): 30.00%
PE-g-MA compatibilizer: 0.50%
Antioxidant packet: 0.30%
Process slider: 0.20%
TOTAL: 100.00%

Application approach:

EVA and PE grades are kept the same in all samples. The D50 value of ATH and surface treatment are fixed. The granule is prepared by controlled mixing. Extrusion torque, surface appearance and thickness are monitored. Tensile, elongation at break and fire screening are performed in the same sample geometry. Additional full system tests are required for the actual cable standard.
Note: Prescription A is the actual control with no ATH. EVA and LLDPE were reduced together during ATH increase.

EXAMPLE 2: APP LEVEL SCAN ON WATER-BASED INTUMESCENT COATING

Purpose: To study the effect of APP amount on film formation, foam-char layer and storage stability in intumescent fire protection coating.

Starting components:

CONTROL A (wt%):

Water-based acrylic binder dispersion: 35.00%
Ammonium polyphosphate (APP): 0.00%
Pentaerythritol (carbon source): 10.00%
Melamine (gas source): 8.00%
Titanium dioxide: 4.00%
Dispersant: 0.50%
Defoamer: 0.30%
Thickener: 0.40%
Preservative: 0.20%
Deionized water: 41.60%
TOTAL: 100.00%

EXAMPLE B (wt%):

Water-based acrylic binder dispersion: 35.00%
Ammonium polyphosphate (APP): 20.00%
Pentaerythritol (carbon source): 10.00%
Melamine (gas source): 8.00%
Titanium dioxide: 4.00%
Dispersant: 0.50%
Defoamer: 0.30%
Thickener: 0.40%
Preservative: 0.20%
Deionized water: 21.60%
TOTAL: 100.00%

Application approach:

The binder is kept constant as the same commercial dispersion; the dispersion's own water is not calculated a second time. APP, pentaerythritol and melamine are homogeneously distributed. The pH, viscosity, precipitation and storage behavior of the paint are monitored. The swelling height, coal layer integrity and fire response of coatings prepared with the same dry film thickness are compared. No protection period is claimed without system testing at the appropriate fire standard.

FLAME RETARDANT ALTERNATIVES AND COMPARISON

The flame retardant alternative is selected based on the material's target fire standard, process temperature, mechanical expectations, smoke and toxic gas criteria. Different chemical admixtures of the same weight should not be expected to perform the same.

FLAME RETARDANT AND ALUMINUM TRIHYDROXY (ATH)

ATH is a halogen-free mineral flame retardant and filler. It can be used especially in some cable and polymer compounds due to its endothermic water release mechanism at the appropriate processing temperature.
When high filler is required, flow, elasticity and final product density can be affected. Surface treatment and particle size must be controlled.

FLAME RETARDANT AND MAGNESIUM HYDROXIDE (MDH)

MDH is also mineral-based system that releases endothermic water; it may be the appropriate option for some polymers that are processed at a higher temperature compared to ATH.
It is not equivalent to the same mass amount of ATH. Segregation, dispersion, hardness, cost and target polymer compatibility are tested together.

FLAME RETARDANT AND AMMONIUM POLYPHOSPHATE (APP)

APP is a phosphorus-containing polymeric flame retardant. It is essential as an acid source in intumescent coatings and can be incorporated into phosphorus-nitrogen combinations in other suitable applications.
Water solubility and particle distribution vary by grade. It should be taken into account that APP will not provide the expected efficacy in pure polyolefins in some cases without synergist.

FLAME RETARDANT AND METAL PHOSPHINATES

Metal phosphinates are special phosphorous flame retardants used in some engineering thermoplastics and glass fiber reinforced systems.
The thermal stability and application grade are different from APP or mineral hydroxides. The manufacturer's grade recommendation should be verified for each resin.

FLAME RETARDANT AND MELAMINE DERIVATIVES

Nitrogenous additives such as melamine, melamine polyphosphate, or melamine cyanurate have different mechanisms. In tumescent coatings, melamine often acts as a gas-former.
The use of melamine alone does not produce the same effect as the tumescent system created with the APP; the identity and proportion of the selected derivative are important.

FLAME RETARDANT AND EXPANDING GRAPHITE

Expandable graphite forms a physical carbon barrier that thickens with heat. Polyurethane can be used in a variety of coatings and composites.
Dark color, particle size, layer orientation, and matrix compatibility may limit its use.

FLAME RETARDANT AND BROMINATED ADDITIVES

Some flame retardants with brominated may be effective with appropriate synergists; however, the regulatory status and environmental-health profile should be checked on a substance-by-substance basis.
Not all brominated products are in the same regulatory status. Halogen-free product is also not automatically non-toxic or superior in every application.

FLAME RETARDANT AND PHOSPHATE ESTERS

Liquid or solid phosphate esters can be used in some polyurethane and resin systems. Some of them may also have a plasticizer or solvent effect.
Its effects on migration, volatility, thermal strength and resin curing are different from those of APP and mineral systems.

QUALITY CONTROL AND PURCHASING CRITERIA FOR FLAME RETARDANT

It is not sufficient to specify the product only as Flame Retardant in the purchase specification. Chemical type, CAS number, manufacturer, commercial grade, active rate, particle size, surface treatment, density, moisture, thermal decomposition, water solubility and target polymer compatibility should be clearly defined.
Documents to be examined: TDS, SDS, COA, REACH and RoHS declarations if applicable, halogen content declaration, relevant SVHC assessment, application-specific technical advice, quality tolerances, shelf life, and packaging information. The carrier polymer and active ingredient percentage for the masterbatch must be specified separately.
Just because the product has passed the laboratory test alone does not mean that the customer's final part will obtain the same grade. Material selection should be based on the final recipe, nominal sample thickness, process, and target standard.
Monitoring moisture, color, bulk density, particle size, and critical impurities in batch acceptance tests can reduce process deviations. Storage stability and moisture resistance are also important in intumescent coating systems.

FLAME RETARDANT STORAGE AND TRANSPORTATION

Dry powder flame retardants should be stored in clean, cool, sealed packages protected from moisture. Even if a low water-solubility grade is used in the APP, attention should be paid to moisture, clumping, and packaging integrity. Spilling mineral powders such as ATH and MDH may create dust accumulation in the work area.
For liquid phosphate esters, solvent-carrying additives, or other liquid systems, flammability, packaging compliance, ventilation, and leakage control must be governed by the product SDS. Not all flame retardants have a single transport class.
The storage periods and recommended conditions of the products may be different. For example, certain shelf life is defined in some APP commercial grades. The current SDS and manufacturer recommendations of the received batch should be taken as a basis, and FIFO and batch tracking should be applied.

FLAME RETARDANT SAFETY INFORMATION

Flame Retardant is not a standard hazard class per se. Hazards depend on the chemical used and its commercial mixture. For solid powders such as ATH or APP, unnecessary dust inhalation and eye contact should be avoided. Some liquid and reactive additives may carry separate toxicological or environmental risks.
High temperature during polymer processing can lead to degradation of the polymer and additive. Volatile degradation products, irritating fumes, or other combustion gases may occur. It should not be assumed that products with added flame retardants produce completely harmless smoke during a fire.
Dust collection, proper ventilation, personal protective equipment, and local occupational health codes should be implemented in the workplace. Formulation waste and fire test samples should be disposed of according to relevant waste management conditions.
The legal status of the substance concerned should be checked through the current target country legislation, especially with regard to certain brominated additives and regulated ingredients.

WHAT TO CONSIDER WHEN BUYING FLAME RETARDANT?

The first question of the procurement process is which polymer or coating and which performance target is desired to be achieved. For example, the mineral filler considered for EVA/PE halogen-free cable does not have to be the right main additive for the steel carrier intumescent coating formulation.
The request should include the final material, target standard, sample thickness, process type/temperature, coloring, mechanical performance, smoke requirements, halogen or SVHC constraints, if any, target price, and estimated annual usage.
Technical comparison should not be made only in kilogram price. The dosage required for equivalent performance, loss of processability, scrap quantity, energy consumption, mechanical strength and long-term quality affect the total cost.
Sample recipes supported by the manufacturer's application laboratory are a useful starting point. However, the final decision should be based on test reports on real samples prepared with the new commercial grade.

FLAME RETARDANT SUPPLY FROM ATAMAN KIMYA

Flame Retardant / Flame Retardant product family; It covers different types of chemical additives used to change fire response in plastic, rubber, cable, construction, coating, foam, textile and composite applications. Appropriate product selection should be made with polymer type, target fire test and process conditions, not with a single general flame retardant name.
Companies requesting the supply of flame retardants from Ataman Kimya can confirm the appropriate additive family, commercial grade, packaging, current stock, origin and price information by sharing their application areas and target technical specifications. The availability of a particular product should be verified separately before sale.
The proposal must include at least the following information: Final polymer/resin; target fire and smoke standard; operating/processing temperature; halogen-free requirement; preferred additive family; target usage quantity; particle size and dispersion requirement; mechanical and electrical requirements; TDS/SDS/COA request and trial quantity.

FREQUENTLY ASKED QUESTIONS ABOUT FLAME RETARDANT

What is Flame Retardant?
It is a chemical additive or additive system used to modify fire response by specific mechanisms.

Is Flame Retardant a single chemical?
It includes ATH, MDH, APP, phosphinates, phosphate esters, melamine derivatives, and other families.

What is the Flame Retardant CAS number?
There is no single CAS number; the chemical type must be specified.

What are halogen-free flame retardants?
ATH, MDH, APP, and suitable phosphorus-nitrogen-based systems are common examples.

Is ATH the same as MDH?
They are two different mineral hydroxides; their thermal behavior and usage conditions are different.

What is an APP?
It is ammonium polyphosphate; it is especially used in intumescent coating and some polymer flame retardant systems.

What is Intumescent?
It is a system that inflates with heat and forms a protective carbonaceous barrier layer.

Why is APP used with pentaerythritol?
APP can function as a source of acid, while pentaerythritol can function as a source of carbon.

What is the role of melamine?
In some intumescent systems, it can be a gas-forming and nitrogenous auxiliary component.

Why is ATH highly available?
In the mineral filling mechanism, high loading may be required for the target performance; the mechanical properties are therefore also optimized.

Is flame retardant product fireproof?
The doped material can retard flame under certain conditions, but it cannot be said to be non-flammable under all conditions.

What does UL 94 V-0 mean?
It is a classification based on vertical combustion testing under specific laboratory conditions; it is not a guarantee of general fire safety.

What is LOI?
It is a laboratory measurement of the lowest oxygen concentration required for sustainable combustion.

Is fire resistance the same as reaction to fire?
The strength of the carrier element and the ignition/flame spread of the material are different evaluations.

Is halogen-free product always smoke-free?
Smoke density and toxicity should be measured separately.

How to calculate flame retardant masterbatch?
It is calculated by multiplying the dosage of the masterbatch by the actual active additive ratio in it.

Is the same recipe used for every polymer?
The polymer chemistry, processing temperature and target standard are different.

Does flame retardant reduce mechanical strength?
It can reduce especially at high filling levels; dispersion and polymer balance are optimized.

What documents are required?
TDS, SDS, COA and target market/application specific legislation and performance documents are required.

Are starter prescriptions certified?
No; they are laboratory screening recommendations and require validation in the final product.

FLAME RETARDANT – TECHNICAL SUMMARY

Flame Retardant is a single non-chemical and broad family of additives that use different fire retardant mechanisms. Appropriate chemical selection depends on polymer/resin grade, process temperature, material thickness, target fire test, and smoke requirements. ATH and MDH are mineral-based endothermic fillers; APP is the important component in phosphorous intumescent systems; metal phosphinates, melamine derivatives, expanding graphite, and some halogenated chemicals offer other solutions.
For this reason, the Flame Retardant statement is not given a single CAS number, molecular formula, density, or universal use level. Each manufacturer grade must be verified with TDS, SDS, and COA. The fire class of a laboratory material does not mean that the final design meets all fire safety requirements.
In this file, ATH percentage screening recipes for halogen-free EVA/PE cable compound and APP percentage for waterborne intumescent coating are proposed. Four separate recipes in both applications are complete to 100 wt%. Dispersion, mechanical and fire performance, aging, and related regulatory requirements must be experimentally validated prior to actual use.

Fire tests do not measure a single performance. UL 94 focuses on the quenching and dripping behavior of small plastic samples in specific geometry and flame application conditions. Classes V-0, V-1, and V-2 must be specified with the measurement conditions. A material of a certain thickness of V-0 does not guarantee the same result for all parts produced thinner or in a different color.
The Limiting Oxygen Index (LOI) determines the oxygen concentration required to maintain the combustion of the material under certain test conditions. An elevated LOI can be a useful indicator; however, low heat dissipation alone does not mean low smoke generation or high safety in all real fire scenarios. Therefore, even when LOI and UL 94 are used together, broader fire characterization may be required.
Methods such as cone calorimetry can provide indicators of heat dissipation rate, total heat release, ignition time, and smoke. While horizontal or vertical small flame tests improve in a formulation, different results can be observed under high heat flux. When comparing tests, radiant heat flux, sample mass, thickness, substrate, and conditioning details should be kept the same.
In building and structural applications, the reaction-to-waste classification and fire-resistance performance are different. While the reaction of the building product to fire is evaluated within the scope of EN 13501-1, the fire resistance of the intumescent coating for steel carriers is determined by the relevant structural element test procedures. A well-intumescent coating in the laboratory cannot claim fire resistance for a certain number of minutes on its own.
Wire and cable applications may have different methods for bundled flame spread, smoke density, gas acidity and halogen content. Since the testing requirements for the end product vary by purchasing industry and country, the exact version of the target standard must be determined in advance when selecting materials.
The technical report must document the product grade, recipe, sample production process, thickness, conditioning, test standard version, number of repetitions and distribution of results. Commercial suitability decisions should not be made based on the good appearance of only one sample.