Iron Oxides in Pigments

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1. Background

This article is based on interviews with 41 pigmentation artists who have used inorganic pigments and hybrid pigments with inorganic bases for over three years and tested their retention and transformation in the skin. A dermatologist, chemist, and an expert in cellular biology have analyzed the artist's observations. This article aims to shed light on using Iron oxides.

General Information

Black Iron Oxide is identified in the Color Index by the code CI 77499 and is an inorganic, hydrophobic pigment. Hydrophobic means that the substance repels water, making it less likely to blend with water-based solutions; it’s water-repellent and not sourced from organic materials. It often falls under the iron oxide category in its second oxidation stage. The chemical formula for Black Iron Oxide is Fe3O4, which uniquely contains iron in both the +2 and +3 oxidation states.

In terms of color, Black Iron Oxide displays a rich, warm hue. It's a lighter color than Carbon Black and tends to shift toward warmer tones over time. This difference in color intensity between Black Iron Oxide and Carbon Black is mainly due to their particle sizes. To make it easy to understand, large particles like Black Iron Oxide appear lighter, while smaller particles like Carbon Black look darker.

2. No "Beauty Industry" Iron Oxides

Iron oxide's purity, particle size, and stability are crucial in semi-permanent makeup. Impurities or poor stability can lead to unexpected color changes or interactions with the skin, while the particle size can affect the color's intensity and longevity. Therefore, understanding the production method is vital for assessing the quality and suitability of the iron oxide used in pigments. There is no specific “beauty industry iron oxide.”

Iron oxides used in the cosmetic industry, including those in semi-permanent pigments, are generally not distinct from those used in other industries. The categorization of iron oxides does not typically differentiate based on the end application, whether it be cosmetics, paints, or coatings.

Iron oxides are compounds composed primarily of iron and oxygen, known for their stability, non-toxicity, and range of vibrant colors. They are widely used as colorants across various industries due to these properties. The key forms include red iron oxide (Fe2O3), black iron oxide (Fe3O4 or magnetite), and yellow iron oxide (FeOOH), among others. The same basic compounds are used across different applications, including cosmetics, paints, plastics, and concrete.

Cosmetic Grade vs. Industrial Grade

While the chemical composition of iron oxides remains consistent across industries, the purity and particle size can vary. “Cosmetic grade” iron oxides, including semi-permanent makeup, are used for cosmetic applications. These are subjected to stringent purification processes to remove impurities like heavy metals, which might be acceptable in paints or coatings but not in products applied to the skin. The particle size is also controlled to achieve the desired color intensity and consistency. However, the fundamental chemical structure of the iron oxide does not change.

Iron Oxides in Various Industries

Cosmetics (including semi-permanent pigments): These are used to color products like foundation, blush, eyeshadow, and semi-permanent makeup. The iron oxides used here are purified to meet safety standards for skin application.

Paints and Coatings. Iron oxides provide color for a variety of paints and coatings. The same iron oxides that give lipstick a vibrant red might be used to paint a barn or coat a piece of machinery, albeit potentially with different purity levels and particle sizes.
Plastics and Rubbers. Iron oxides are used to color various plastic and rubber products. Their robustness and stability make them suitable for these applications.
Concrete and Building Materials. Iron oxides are used to color concrete products and other building materials, providing an array of aesthetic options.

While the base chemical may be the same, the cosmetic industry requires iron oxides that meet specific safety standards. Cosmetic-grade iron oxides undergo processes to ensure they are safe for prolonged contact with the skin, do not contain harmful impurities, and provide consistent and predictable color. The particle size is often smaller and more uniform, providing a smoother application and finish suitable for cosmetic products.

While iron oxides' basic chemical structure remains consistent across various industries, the specifics of their processing and purification differ significantly when used in cosmetics.

3. Production Methods of Iron Oxide

Various methods are utilized to produce iron oxide for colorants. Each method has its unique benefits and influences the properties of the resulting iron oxide nanoparticles. Here's an overview of the most common production techniques.

Inverse Microemulsion

This process involves creating a microemulsion where the aqueous phase is dispersed in the organic phase, leading to nanoparticles of controlled sizes. It's particularly useful for creating iron oxide nanoparticles with specific properties.

Sol-Gel Synthesis

This chemical process typically starts with a colloidal solution (sol), the precursor for an integrated network (gel) of discrete particles or network polymers. It allows doping iron oxide with other elements to alter its properties, making it versatile.

Flow Injection

Though often used in analytical chemistry, its application in synthesizing iron oxides is less common. It involves rapidly injecting reactants into a flowing stream to create iron oxide particles.

Electrospray Synthesis

This method uses an electric field to create fine particles from a liquid solution, producing iron oxide nanoparticles with a high degree of control over size and morphology.

Sonochemical Method

This method utilizes ultrasound energy to induce reactions, which is valid for producing iron oxide nanoparticles. The acoustic cavitation produced by ultrasound can generate the extreme temperatures and pressures needed to form these particles.

Hydrothermal Synthesis

Widely used for producing a variety of iron oxides, it involves reacting raw materials under high water pressure and temperature in a sealed vessel, typically an autoclave. This method is known for producing materials with high purity and crystallinity.

Thermal Decomposition

This method involves heating a precursor to decompose it into iron oxide, often producing nanoparticles with excellent control over size, shape, and crystallinity.

Coprecipitation Method

One of the simplest and most efficient methods for synthesizing iron oxide nanoparticles involves the simultaneous precipitation of Fe2+ and Fe3+ ions in an alkaline medium.

Mechanical Milling

This solid-state mixing of powders is used to prepare more complex or mixed-phase materials such as spinel or magnetite.

Although many production methods exist for obtaining iron oxides, a shorter list is generally viable for producing iron oxides used in semi-permanent pigment colorants. In producing iron oxides for semi-permanent pigmentation pigments, the choice of synthesis method significantly impacts the purity, particle size, morphology, and consequently, the safety and suitability of the iron oxides for cosmetic use.

4. Use in the Beauty Industry

Thus, methods generally considered viable for beauty industry-grade iron oxide production include the following.

Sol-Gel Synthesis

This method is promising for cosmetic applications because it produces iron oxides with controlled particle sizes and shapes. The sol-gel process can create iron oxide nanoparticles with high purity, which is crucial for minimizing adverse skin reactions in semi-permanent makeup.

Hydrothermal Synthesis

This method is also suitable for producing high-purity iron oxides. Hydrothermal synthesis's controlled temperature and pressure conditions allow for the production of well-defined and uniform particles. The purity and consistency of hydrothermal synthesis make it a viable option for creating iron oxides for semi-permanent pigmentation.

Thermal Decomposition

This method can produce highly pure iron oxides with controlled particle sizes. The high-temperature conditions involved in thermal decomposition facilitate the removal of impurities, which is crucial for products applied to the skin. The resulting iron oxides from this method could be suitable for semi-permanent pigmentation, provided they undergo rigorous post-synthesis purification.

Sonochemical Method

While less common, the sonochemical method can produce small and uniform nanoparticles. If the process is carefully controlled and followed by thorough purification, the iron oxides produced could be used in semi-permanent pigmentation pigments. However, the scalability and control of particle characteristics need to be considered.

Importance of Removing Impurities

It's essential to note that regardless of the synthesis method, any iron oxide intended for use in semi-permanent makeup must undergo rigorous purification to remove impurities, particularly heavy metals. They must also be finely milled to achieve the appropriate particle size for cosmetic use, ensuring a smooth application and minimizing the risk of adverse skin reactions.

Moreover, post-synthesis processing, including sterilization and testing for biocompatibility and allergenicity, is crucial. The final product should adhere to strict regulatory standards for cosmetics to ensure safety and efficacy.

In practice, the choice of method will depend on factors like the desired properties of the iron oxide, cost, scalability of the process, and the manufacturer's capability to ensure the purity and safety of the final product. As a professional in this field, you'd seek to balance these factors, prioritizing the safety and satisfaction of the end-users receiving the semi-permanent pigmentation treatments.

5. Synthetic Production - A Standard

Some producers introduce pigment lines that contain iron oxides, sometimes touting them as produced with “revolutionary” or “next-generation” methods. These claims should be critically evaluated. While some claims may be unfounded or exaggerated, others could indicate real improvements, particularly in purification processes.

For instance, marketing descriptions of pigments containing iron oxides as being produced “synthetically” are not groundbreaking. Synthetic production of iron oxides for the cosmetic industry, including pigments, has been standard practice for decades, dating back to the early to mid-20th century.

The transition from natural iron oxides (extracted directly from iron ore) to synthetic ones occurred primarily because synthetic methods can produce purer, more consistent, and safer products. In cosmetics, especially in applications as sensitive as semi-permanent pigmentation, the purity and consistency of the pigment are paramount for safety and performance. There's no knowledge of a producer extracting iron oxides for cosmetic pigments directly from iron ore due to the impracticality of controlling impurities like heavy metals in natural iron oxides, making synthetic production the preferred and standard method for cosmetics.

Problematic Natural Methods

Producing iron oxides from natural iron ore is generally less expensive than synthetic methods, mainly because it involves direct extraction and processing of the ore. However, the lower cost of natural iron oxide production is outweighed by significant disadvantages for cosmetic use, including inconsistency in color, impurities, and the potential presence of toxic elements. Synthetic production, albeit more costly, offers control over the iron oxide's purity, particle size, and color, crucial for applications like semi-permanent makeup where safety and color consistency are critical. These stringent requirements and the superior quality of the final product justify the higher cost of synthetic production.

Progress in Synthetic Production

While there haven't been abrupt revolutionary changes in the production of synthetic iron oxides, significant evolutionary advancements have improved their quality and safety. These advancements include the following.

Enhanced Purity and Consistency. Improvements in synthetic methods have allowed for the production of iron oxides with higher purity and more uniform particle sizes, essential for consistency and safety in cosmetic applications.
Customization of Particle Size and Shape. Advances in synthesis techniques like sol-gel, hydrothermal, and thermal decomposition have enabled the production of iron oxides with specific particle sizes and shapes, allowing for tailored application properties in semi-permanent makeup.
Greener Synthesis Methods. There's a growing focus on more environmentally friendly synthetic methods that reduce waste and energy consumption, reflecting a broader industry trend toward sustainability.
Regulatory Compliance. As regulations around cosmetic ingredients have become more stringent, synthetic methods have adapted to ensure that iron oxides meet the highest safety standards, including minimizing heavy metal content and other impurities.

While not “revolutionary,” these advancements represent significant progress in the field, continually enhancing the safety, performance, and sustainability of iron oxides used in semi-permanent pigmentation and other cosmetic applications.

6. ECHA Compliant - “Empty” Term

When an iron oxide is described as "ECHA compliant," it's somewhat of a misnomer or marketing term. The European Chemicals Agency (ECHA) is the regulatory body responsible for enforcing REACH and other chemical regulations in the EU. It does not directly "issue" REACH but is tasked with its implementation and enforcement. Therefore, "ECHA compliant" isn't officially recognized or defined.

The correct and meaningful term is "REACH compliant." If a pigment is to be sold within the European Union, it must comply with REACH regulations. Since ECHA oversees REACH compliance, a substance that meets REACH criteria effectively complies with ECHA's enforcement of EU chemical regulations. In this sense, while the phrase "ECHA compliant" is not formally defined, a pigment meeting REACH requirements complies with the standards and regulations enforced by ECHA.

Thus, while "ECHA compliant" might be used in marketing to suggest regulatory adherence, the substantive and recognized term reflecting compliance with EU chemical regulations is "REACH compliant." A REACH-compliant pigment is, by extension, compliant with the standards enforced by ECHA.

Difference Between ECHA and REACH

Therefore, ECHA (European Chemicals Agency) is the regulatory agency responsible for implementing chemical legislation in the European Union. It oversees the enforcement of various chemical regulations, including REACH.

REACH (Registration, Evaluation, Authorisation, and Restriction of Chemicals) is a regulation of the European Union designed to improve the protection of human health and the environment from the risks posed by chemicals. REACH places the responsibility on companies to manage the risks and provide safety information on the substances they produce or import into the EU.

In simple terms, ECHA is the agency, while REACH is one of the regulations that ECHA enforces.

7. REACH Compliance

REACH itself does not specifically restrict the use of iron oxides. Instead, it establishes a comprehensive framework for registering and evaluating substances to ensure their safety for human health and the environment. Under REACH regulations, all chemicals, including iron oxides, must be registered with ECHA, accompanied by detailed information on their properties, uses, and guidelines for safe handling.

Although REACH does not set explicit criteria for the "purity" or "cleanliness" of iron oxides, it mandates the identification of hazardous impurities and implementing measures to manage their risks. Companies must also comply with applicable restrictions and guarantee safe usage throughout the supply chain. For iron oxides utilized in cosmetics, additional standards for purity and safety are specified by the EU Cosmetics Regulation, underscoring the need for higher purity levels for human use. Thus, while REACH does not directly limit iron oxides, it demands thorough safety assessments and compliance with relevant restrictions to ensure their safe application.

Getting REACH Compliance

Manufacturers who have achieved REACH compliance often state that reasonably high-quality iron oxide for pigments considerably eases compliance. In practical terms, attaining REACH compliance typically involves securing a detailed chemical analysis from a certified laboratory within the European Union. This analysis must verify that the iron oxide sample does not contain toxic elements beyond the limits set by REACH regulations.

The manufacturer is responsible for keeping the documentation to prove that the pigment's composition meets established safety standards. Suppose the sourced iron oxide is of good quality and its chemical composition falls within REACH's specified thresholds for hazardous substances. In that case, reaching compliance is a matter of following correct procedural steps, including thorough and precise laboratory analysis and maintaining proper records. In summary, with high-quality iron oxide, achieving REACH compliance becomes a largely procedural task that is "hard not to get," provided all regulatory requirements are met diligently.

8. Producers vs. Brand Owners

Most brand owners in the pigment market identify as “producers” yet do not manufacture their components directly. They do not usually own the industrial facilities to synthesize or significantly alter raw materials like iron oxide. Instead, these brands typically function as intermediaries, sourcing pre-made components from global manufacturers specializing in pigment production. This model enables them to concentrate on branding, marketing, and distribution, leveraging the quality standards of their suppliers.

Reliance on Supplier Quality Standards

These brand owners heavily depend on their suppliers' reputations and quality assurance protocols. They trust that the iron oxide and other components they purchase comply with purity and safety standards. This dependency highlights the critical role of supplier selection in preserving product quality and safety. Brand owners must carefully vet their suppliers to ensure the procured materials meet their market's regulatory requirements and quality expectations.

Capabilities of Actual Producers

Only entities that possess and operate the manufacturing facilities and the necessary certifications can rightfully claim to modify or purify components like iron oxide. These producers possess the technical know-how and regulatory approval to process raw materials, potentially eliminating unwanted impurities or modifying properties to satisfy particular standards. Their assertions of 'purification' or modification are based on the physical and chemical processes executable within their certified facilities.

The “Impossibility" of Non-Compliance

Iron oxide, in its raw form, is not listed among the substances restricted by REACH. Thus, iron oxide would typically be regarded as REACH-compliant unless it is tainted with impurities or additives subject to REACH restrictions. While REACH does not prescribe specific “quality standards” for iron oxide regarding purity or performance, a pigment formulation that includes components restricted by REACH could render the entire formulation non-compliant. Compliance for pigments, therefore, hinges not solely on the iron oxide utilized but also on the complete composition of the pigment and its conformity with REACH regulations.

9. *Conclusions

Iron Oxide in the Cosmetic Industry

The "revolutionary transformations" claim in producing iron oxides for semi-permanent makeup leans more towards marketing than scientific advancement. Iron oxides in cosmetics are chemically the same as those in other industries, with no exclusive "cosmetic grade" distinction. The differentiation lies in the stringent requirements for purity, particle size, and safety in cosmetics.

Quality and Compliance of Iron Oxides

Pigment producers must ensure their iron oxides meet critical criteria: high quality, consistent and small particle size, and compliance with legal limits on toxic substances. All modern iron oxides are synthetically produced, making the claim of "synthetically produced iron oxide" redundant, as natural extraction is outdated.

Production Methods

Key methods for producing iron oxides suitable for semi-permanent makeup include Sol-Gel Synthesis, Hydrothermal Synthesis, Thermal Decomposition, and the Sonochemical Method. Advances in particle size control and purity enhancement have been made, essential for cosmetic pigment safety and efficacy.

Regulatory Compliance

In the EU, pigment substances must comply with REACH regulations the European Chemicals Agency (ECHA) enforced. A pigment's "REACH compliance" indicates adherence to ECHA's standards, making the term "ECHA compliant" misleading and unnecessary.

Iron Oxide REACH Compliance

REACH does not specifically limit the use of iron oxides. Issues may arise from other pigment components under REACH restrictions.

Claims of Purity and Quality

Claims regarding the purity and quality of iron oxides require independent verification. Producers without manufacturing capabilities typically source quality iron oxide from global suppliers, and claims of further purification by these producers are often unfounded without specialized facilities.

While the semi-permanent makeup industry relies on high-quality, pure iron oxides, marketing often misrepresents the scientific and production reality. Understanding synthetic production, regulatory compliance, and innovation in iron oxide production is crucial for professionals and consumers. Ensuring safety and quality standards remains paramount for end-user well-being.