Titanium dioxide (CI 77891)

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3. How is titanium dioxide made?

Sulfate Process

The sulfate process is an older, less efficient method for producing titanium dioxide. In this technique, ilmenite (FeTiO3) is mixed with concentrated sulfuric acid at around 100°C.

FeTiO3+2H2SO4→FeSO4+TiOSO4+2H2O

In the next stage, iron(II) sulfate, a by-product, is removed through filtration. To facilitate this, the entire process is cooled to 15°C, causing the iron(II) sulfate to crystallize, making it easier to remove via filtration. The remaining TiOSO4 is then heated to 110°C and hydrolyzed.

TiOSO4+(n+1)H2O→TiO2×nH2O+H2SO4

As a result of hydrolysis, a sulfuric acid residue, and hydrated titanium dioxide are produced. In the final stage, the hydrated TiO2 is heated in a rotary kiln to remove water and form anatase and rutile crystals.

TiO2×nH2O→TiO2+nH2O

Water is removed within a temperature range of 200–300°C. Seed crystals are added to the titanium dioxide to initiate the crystallization process. Depending on the final temperature, either rutile crystals (800–850°C) or anatase crystals (900–930°C) are formed. Generally, synthetic rutile is the end product.

The process requires large amounts of sulfuric acid and produces significant sulfuric acid waste. If not managed properly, this waste can be detrimental to the environment.

The ilmenite ore is also utilized to produce synthetic rutile using the Becher process. In the Becher process, redox reactions are carried out to ensure the purity of the end product, which is then treated with air and drained.

Chloride Process

The chloride process is a more modern and efficient technique for producing titanium dioxide. This method necessitates high-grade rutile ore containing at least 70% rutile. The titanium dioxide is first reduced with carbon and then chlorinated.

TiO2+C→Ti+CO2

Ti+2Cl2→TiCl4

The liquid titanium tetrachloride (TiCl4) is then distilled and converted back into titanium dioxide. This is achieved by oxidizing the titanium tetrachloride in a pure oxygen flame or plasma at temperatures ranging from 1200–1700°C.

TiCl4+O2→TiO2+2Cl2

As a result, a large portion of the chlorine used in the process is regenerated. This method often produces a purer and higher quality product than other techniques.

While the chloride process utilizes large amounts of hazardous gaseous chemicals like Cl2 and TiCl4, it also requires significant thermal energy. The process may produce toxic gases like chlorine and sulfur dioxide, unreacted solid and liquid mineral residues, and various chloride compounds. Despite the potential environmental risks posed by these substances, the chloride process has been favored since the 1990s, mainly for financial reasons.

Production of Nanostructured Titanium Dioxide

The production of nanostructured titanium dioxide involves using liquid titanium tetrachloride (TiCl4). The TiCl4 is evaporated by heating and then mixed with air and hydrogen. These gases are heated in a burner at high temperatures, ranging from 1000–2400°C, initiating a reaction. During this process, tiCl4 is converted into titanium dioxide, and gaseous hydrogen reacts with chloride ions to form hydrogen chloride (HCl).

TiCl4+2H2+O2→TiO2+4HCl

The resulting titanium dioxide is pure and consists of nanoparticles with an approximate diameter of 21 nm. Whether these particles are suspended in a liquid or coated onto a glass surface, they are so small that they are invisible to the human eye. Moreover, both the liquid and the glass remain transparent due to the nanoparticle size.

Particle size in Powder Brows pigments

The particle size of CI 77891, also known as titanium dioxide, in an inorganic pigment mix can vary depending on the application and manufacturing process. However, it's commonly found in the range of 200 nm to 350 nm, sometimes even up to 400-500 nm for pigmentary applications, often the size being 200-250 nm. These particle sizes are much larger than those used in nanostructured titanium dioxide, which can be as small as 21 nm as mentioned earlier. The larger particle size in pigment applications provides optimal scattering of visible light, which is desirable for achieving high opacity and brightness, crucial properties for many pigmentation uses.

Importance of Purity and Quality

The quality of the titanium dioxide can differ depending on the processing method and the raw materials used. Higher purity is often desired for applications like cosmetics and pharmaceuticals, where any impurities can have undesirable effects.

In some cases, titanium dioxide is further processed to make it suitable for specific applications. For example, it can be coated with silica or alumina for better dispersion in certain mediums. In cosmetics, achieving the right particle size and shape is important for optimal skin coverage and minimal skin irritation.

Thus, the journey of titanium dioxide from its natural mineral form to the fine, white powder used in pigmentation involves various extraction and purification steps.

4. Where is titanium dioxide found?

Titanium dioxide, often labeled as E171 in Europe or simply as a "color additive" in the United States, is commonly used in everyday foods and other products. Its primary purpose is to act as a whitening agent, giving products a cleaner, brighter appearance. You can find it in the following.

Food Products and sweets

You can find titanium dioxide in many types of candies, particularly those that are white or brightly colored. It's often added to cakes, cookies, and donut icing to make it look whiter and more appealing. Titanium dioxide is used to give chewing gum its white color. Pre-packaged snacks like chips and crackers may contain this additive for color stabilization. Some types of yogurt, cheese, and other dairy products use titanium dioxide to maintain a consistent, appealing color. It serves as a colorant in certain drinks, like dairy-based coffee creamers.

In January 2022, the European Commission passed a law prohibiting using titanium dioxide (E171) in food. This law allows food items with titanium dioxide to be made only up until August 7, 2022. After this deadline, these products can still be sold, but only until their "best before" date runs out. As of May 2023, following the European Union's 2022 ban, the U.S. states of California and New York are also contemplating a ban on titanium dioxide in food products.

A cupcake with white icing, white cheese, and a tube of a cosmetic product on the left, and an attractive girl with gray hair on the right.

A cupcake with white icing, white cheese, and a tube of a cosmetic product on the left, and an attractive girl with gray hair on the right.

Personal Care Products and Cosmetics

Titanium dioxide is the substance that gives your toothpaste its bright white color. It is often used in physical sunscreens to reflect UV rays. In cosmetics, it's commonly found in various makeup products, including foundation, powder, and lipstick, often to provide sun protection or for its coloring properties.

Other Household Items

Regarding other household items, it can be found in paints, which are widely used to give paints a bright, white base. Many plastic items like utensils and furniture can contain titanium dioxide for coloration and durability. It's used in some types of high-quality paper to give it a smoother, whiter appearance.

While generally considered safe, there is ongoing research into the health impacts of titanium dioxide, particularly in its nano-form. Some countries have started reassessing the safety of food products. Always check product labels if you have concerns about this ingredient.

5. Positive sides of titanium dioxide

Better longevity of the pigment

Titanium Dioxide is a prevalent additive in semi-permanent makeup pigments, particularly in lip and sometimes eyebrow pigments. Its main function is to increase the pigment's reflectivity, enhancing the longevity and stability of the color over time. By doing so, it helps to prevent the pigment from shifting into undesirable hues as it ages.

Stable, Brighter Colors

Many experienced artists report that pigments containing titanium dioxide yield more stable and enduring results. Beyond the white color that titanium dioxide provides, the other shades in the pigment also tend to remain stable within the skin. This allows for a more consistent color application over time. For procedures like eyeliner and lip coloring, the results are vivid and do not fade into duller versions as quickly. Specifically, when discussing lip pigments, many seasoned artists find that including titanium dioxide produces superior, more vibrant results. These outcomes are generally less achievable, with organic-based pigments needing more titanium dioxide. However, that applies to cases where the concentration of titanium dioxide is not too dominant in the pigment.

Predictable Fading The fading process with titanium dioxide-based pigments tends to be more predictable and gradual. As the pigment fades, it generally lightens uniformly over time. This even lightening is partly because titanium dioxide remains present in the skin for longer periods. Essentially, as the concentration of the colored pigment decreases, the ratio of white titanium dioxide molecules to other colored molecules shifts. This results in a clearer, more consistent fading process throughout the various healing phases.

Why does the titanium dioxide make pigments stay brighter?

The physical reason behind titanium white's effect is its high refractive index. This property allows it to scatter light effectively, making the pigment appear brighter and more opaque. This high-opacity attribute enables the pigmentation colors to achieve their desired, true-to-tone color in fewer passes. Titanium white's physical characteristics also contribute to the pigment appearing dull and bleached, as opposed to more transparent and translucent when the ingredient is absent.

What are the chemical positive sides of titanium dioxide?

On a chemical level, titanium dioxide is a stable compound that does not easily react with other elements. This stability helps preserve the pigment's original color, affecting its metabolization in the skin. If a pigment containing titanium white is poured into water and left for an extended period, it will separate and settle at the bottom, demonstrating its chemical stability and low solubility in water.

The presence of titanium white can also influence the temperature of the pigment; it tends to lend a cool undertone to the color. This is important to consider when choosing pigments, as it can affect the final appearance of the semi-permanent makeup. Thus it can be said, that titanium white contributes to opacity, brightness, and stability. It grants a stable healing process and repeatable results.

6. Negative aspects of titanium dioxide

An attractive young woman with gray hair on the left, the sign of infinity, laser beam, and a horror movie-style clown face on the right.

Longer retention in the skin

The most notable downside of using titanium dioxide in semi-permanent makeup pigments is its long-term retention in the skin. Titanium dioxide persists in the dermal layers, unlike other pigment components that gradually fade due to various factors.

Why do other colorants fade but not titanium dioxide?

Over time, the colors of pigments tend to fade due to several mechanisms. Ultraviolet (UV) radiation from the sun can degrade the pigments, altering their molecular structure and leading to color loss. Additionally, the body's immune system actively identifies and attempts to remove foreign substances, including some pigments, as part of its natural defense mechanism.

Physically, titanium dioxide particles are larger and have a high refractive index, allowing them to scatter light more effectively. This characteristic makes them more visible and harder to break down. Furthermore, these particles create a chalk-like substance in the dermis, which tends to adhere more robustly to the surrounding skin tissues.

The negative side of excellent stability

Chemically, titanium dioxide is a very stable compound. It is inert, meaning that it does not readily react with other substances. This chemical stability makes it resistant to degradation, whether from UV radiation or enzymatic processes within the skin. The body's immune system does not recognize titanium dioxide as a foreign substance that must be eliminated, so it remains in the skin over the long term.

It's inaccurate to say that titanium dioxide stays in the body indefinitely, but it lenses in the skin significantly longer than other pigment colorants. Therefore, the most common approach to address this is to refresh the pigmentation periodically. Doing so helps to keep the color stable and vibrant for an extended period.

Resistance to laser removal

The challenge of removing titanium dioxide from the skin becomes evident when attempting to use laser removal methods. The substance resists conventional laser removal for several reasons. Physically, titanium dioxide has a high refractive index, making it less susceptible to absorption by lasers. Therefore, laser removal often darkens pigments containing red oxide and titanium dioxide instead of eliminating them.

Semantical claims regarding being “cancerogenic”

It's true that the International Agency for Research on Cancer (IARC) has classified titanium dioxide as a Group 2B carcinogen, which means it's "possibly carcinogenic to humans." However, this classification applies primarily to inhaling titanium dioxide dust, particularly in industrial settings. The U.S. National Institute for Occupational Safety and Health (NIOSH) also recommends specific exposure limits to titanium dioxide particles in the air.

Larger quantity in lip pigments = bigger risks

A picture of "nude" lip color lips on the left, an attractive young woman with gray hair in the middle, and a picture of a dark-skinned woman with very dark, almost black lips on the right.

As discussed in this article, regarding lip pigments, professionals are generally not too critical of titanium dioxide because it can enhance the color, making it appear more vibrant. However, as said, that only applies is the quantity is moderate.

Good for the nude effect

It's crucial to look at the color index when choosing a lip pigment that contains titanium dioxide. If the titanium dioxide color index (CI 77 891) is listed in the first position, it usually means that the pigment contains a high concentration of this compound. In such cases, it's advisable to proceed with caution. Such pigments are best suited for clients with very light natural lip colors or those aiming for a nude effect.

Often Not optimal for the dark skin

Further caution is advised for certain skin types, particularly those at the darker end of the Fitzpatrick scale, such as types 5 and 6. Some dermatologists have warned that a high concentration of titanium dioxide in lip pigments can result in unwanted effects during the healing process. Specifically, the lips may heal to a black color.

7. Titanium dioxide in brow pigments

On the left, there is soap residue on a black surface with the word "BROWS" on it, and on the left, there is a young girl with gray hair.

No real need to be included

In the realm of brow pigmentation, many professionals suggest not to use pigmetns with titanium dioxide. One has to realize that titanium dioxide is commonly used to lighten the tone of the pigment. When added to a pigment mix, titanium dioxide essentially "dilutes" the color, making the result appear lighter than it would without it. In other words, it lightens the color to a degree, often by a tone.

In the context of eyebrows, there's generally no requirement to make the tone lighter. Despite this, some manufacturers include titanium dioxide in their formulations, often using it as a filler material. This could be a cause for concern, particularly during the healing process.

Potential problems with healing

The problem manifests after the treatment, during the skin's natural healing cycle. As the colorant components of the pigment gradually fade or metabolize, you're left with the inorganic titanium dioxide. This can result in a patchy and uneven light gray shade. The outcome is a "light dirty grayish" appearance, akin to a black color that seems to be veiled with a semi-transparent film, almost like soap residue. This effect creates a patchy and uneven look, with some darker spots being more prominent than others.

So, if you're an artist or a consumer considering a brow pigment, it's worth knowing that many professionals prefer not to use it for the above-mentioned reasons.

8. Nanoparticles vs. pigment particles

Differences in Particle sizes

In nanoparticle form, titanium dioxide particles usually range from about 10 to 100 nanometers in diameter. Particles of titanium dioxide used in pigments for applications like semi-permanent makeup are typically much larger. These can range from around 200-300 nanometers to a few micrometers (1 micrometer = 1000 nanometers); as mentioned in this article, those are typically around 200-250 nm, sometimes up to 400-500 nm.

Thus, when it comes to the use of titanium dioxide in semi-permanent pigments, the size of the particles matters significantly. The concerns about the carcinogenicity of titanium dioxide mainly involve nanoparticles, which are not typically used in pigments for semi-permanent makeup. The particles in such pigments are much larger, which changes their interaction with biological tissues.

That said, it's worth noting that as of my last update in January 2022, there is still ongoing research concerning the safety of titanium dioxide in various forms and applications, including its potential role in diseases like inflammatory bowel disease and colorectal cancer. However, these concerns have not been definitively proven to extend to the larger particles of titanium dioxide used in semi-permanent makeup pigments.

Different effects

So, while there is a basis for concern about the potential carcinogenic effects of titanium dioxide, these concerns are not directly transferable to its use in semi-permanent pigments, owing to the difference in particle size. The marketing strategies that label titanium dioxide as unequivocally "carcinogenic" may overstate the case based on the current scientific understanding.

9. Removal of titanium dioxide

Regarding the best practices for removing titanium dioxide, the most effective approach usually involves using a removal system consisting of various acids and salts. These substances can break down the granulated pigment particles in the skin, making it easier to remove them. The removal process needs to be done in multiple sessions for optimal results. The exact number of treatments varies based on the makeup's intensity, the type of pigment, and the depth at which it was applied.

Following a removal session, typical reactions include some bleaching. This is due to the release of gas when the pigment is heated during the process. You can repeat each removal session as soon as six weeks have passed. One significant advantage of this method is its effectiveness in removing more colors than lasers, even very dark pigmentation, which are primarily effective on black, red, and gray pigments only. Thus, with such compounds, opting for a chemical remover is usually the more effective route.

So, while laser removal has its limitations, especially when dealing with pigments containing titanium dioxide, other more specialized removal techniques can be more effective.

10. Marketing wars

One must not be naive and understand how different producers manipulate the situation, both those who use titanium dioxide and those who don't. They use semantic tricks to either hype it up or label it as the "super-villain" of all colorants.

Longevity in the Body

It's true that titanium dioxide tends to stay in the body for a longer period compared to some other substances. However, it's not alone in this regard. Other chemicals and colorants used in permanent makeup (PMU) also have similar properties.

Questioning Claims

When you hear claims from artists or marketers about pigments, always approach them with a critical mindset. Understand that these individuals often have a financial stake in promoting their products. So, they might emphasize the positives of what they're selling while downplaying the negatives.

Pro-Titanium Dioxide View

Artists who prefer using titanium dioxide and are affiliated with makes who use it often highlight its benefits. They may talk about the brighter, more vibrant results it delivers. On the flip side, they'll often criticize other dyes' drawbacks or potential health risks.

Anti-Titanium Dioxide View

Those who steer clear of titanium dioxide tend to label it as a "cheaper option," "questionable," or even "harmful." They might also claim it to be carcinogenic, even though the particle sizes typically used in pigments are generally larger and less reactive than their nanoparticle counterparts.

Balanced Perspective

All things considered, titanium dioxide, is not the "arch-nemesis" of PMU colorants that some make it out to be. In fact, other elements like carbon or even precious metals like gold can be harmful or pose health risks if manipulated into certain sizes or forms.

That being said, it's crucial to recognize that titanium dioxide does stay in the body for an extended period. The artist and the client must know this before proceeding with any pigmentation work. They should have a clear plan for future touch-ups or be prepared for the extended time it may take to remove the pigment.

By considering these various aspects, you can make a more informed decision about using titanium dioxide in PMU or other applications.

11. Conclusions

Titanium dioxide is an inorganic component sourced from the Earth's crust minerals. It has a relatively large particle size (about 300 nm). It is one of the most common colorants in our everyday life, and most of us come into contact with different forms of titanium dioxide daily. It is used in many sweets, chips, cheese, and yogurt. While the EU has banned its use in food products, it remains a common food colorant in the rest of the world. Additionally, it is often found in toothpaste, sunscreens, pills, paper, and paints to make them white.

In the realm of semi-permanent makeup, pigments with titanium dioxide offer many positive aspects: better longevity, stable brighter colors, and predictable gradual fading. However, there are downsides to consider. These include its long retention in the skin, resistance to laser removal, and semantic claims labeling it as unhealthy (or even "carcinogenic"). While it is true that titanium dioxide is harder to remove than many other colorants, chemical removers can effectively eliminate it.

All things considered, it's just another substance used in pigments without considerably worse effects on health compared to other substances. However, its long retention time should certainly be considered and discussed with the client when an artist uses a pigment containing it.

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Origin of Titanium Dioxide

3. How is titanium dioxide made?