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Metallic bowls, foils and hair bleach

Q.  The instructions in the bleach I use indicate I should not mix bleach in a metallic container, I am assuming this means all types of metal bowls.  If that is the case why is it acceptable to place the bleach and hair between two pieces of foil (metal)? Andre, San Pedro, CA.

A. The cautionary note against mixing bleach in metallic bowls dates back to the time when bowls were made mostly of copper or iron. Copper and iron were quite common and inexpensive materials prior to the commercial introduction of plastics and the availability of affordable stainless steel.

Copper and iron bowls can oxidize or rust very easily and can result in very active metallic ions (strong catalysts) that may leach into any liquid medium contained in these bowls. Because of these strong catalysts, bleach mixtures prepared in these metallic bowls frequently break down and lose their lifting power.

Stainless steel on the other hand, does not have this problem because it does not oxidize easily and does not leach active ions into the bleach. Similarly, aluminum also is stable and resists oxidation and leaching of active ions. That is why the aluminum foils that come in contact with the bleach on the hair are harmless and do not affect the bleaching action.

Therefore, to guard specifically against the possible use of rusty iron or copper metallic bowls with hair bleaches, manufacturers include the cautionary note in their bleaches against all metallic bowls. This would be a much safer approach than saying, for example, “Mix only in oxidation-resistant metallic bowls”.

Hair color removers

Q: Dr. Said, could you kindly explain to me how hair tint removers work, and are they all the same? Thank you. Molly, Charlotte, NC

A:  In permanent hair tints, dye precursor intermediates (called primaries and couplers, which are by themselves colorless) are coupled and locked in place by hydrogen peroxide to produce colored dye molecules. These colored molecules can be removed by two different processes: Either by a process involving reducing agents; or by a process involving oxidizing agents.

The first process, especially effective against permanent hair color, utilizes reducing agents like sulfites or thioglycolates, which act in a manner opposite to hydrogen peroxide. As mentioned above, hydrogen peroxide locks colorless dye intermediates together to produce color. Reducing agents like sulfites unlock the color molecule (undoing what peroxide did), resulting in the loss of color.

The second process involves the use of strong oxidizers such as bleach. These oxidizing agents are strong enough to permanently change the structure of the dye molecules and therefore destroy the color.

Each of these two processes has its advantages and disadvantages. Color removal by reducing agents is generally a milder process. However it requires that the reduced (unlocked) dye molecules be completely washed out of the hair (which is not an easy task) otherwise air, which is by itself a mild oxidizing agent, would re-lock the color molecule and restore color. That is why some products appear to remove the color on day of application only to have the color come back a couple of days later.

Color removal by strong oxidation (bleaching) on the other hand is more effective because the dye molecule is damaged beyond repair. But care should be taken not to cause excess damage to the hair in the process

Needless to say that neither process for color removal is totally effective. Some hues remain in the hair to different levels after either process but these generally are not of major concern if the hair is to be colored again.

It is always crucial to follow the manufacturer’s instructions for the product being used to achieve maximum results.

Effect of oxidizers on hair dyes and hair melanin

Q. Dr. Said, I was wondering if you could give me a description of how oxidation opens the cuticle, disperses the melanin and binds the intermediates. As I have heard it has to do with the covalent bonds of the Oxygen and Hydrogen and the heat produced by the exchange of atoms. I have never had a chemist explain the process to me and I am very interested in knowing the specifics. Also, how are eumelanin and pheomelanin different from each other and is melanin ever gone completely and eliminated from the hair? Robin, San Diego, CA

A. Oxidation has only a minor role in opening up the cuticle. It is rather the alkaline base (in the form of ammonia or monoethanolamine) that causes swelling and loosening of the cuticle. Oxidation works progressively on melanin to bleach the color and causes irreversible changes in the melanin molecule and also to oxidize the dyes.

Dye intermediates undergo oxidation by the peroxide to form larger colored dye molecules. Dye intermediates by themselves are colorless. When a primary dye intermediate is oxidized, it loses hydrogen atoms and becomes activated so that it attacks a second dye intermediate in the form of a coupler or even another primary and binds to it covalently (strong bonding). This may be repeated more than once and the resulting molecule grows larger.

What you have heard about covalent bonds between hydrogen and oxygen, and about heat production is so general and vague that it does not help you understand the specifics of the chemical reactions involved. However don’t feel left out because you are not alone. Suffice to know that for a chemical reaction to take place, the products of a chemical reaction must achieve a lower energy level (or are more at ease) than the starting reactants which are (tense or edgy). It is like trying to push a rock downhill but before you are able to get it to the edge of the hill (where it can roll down on its own), it has to climb a small mound of dirt. In doing so you have to give it a push and spend some energy. In hair color, the push over the small mound of dirt that your rock  has to overcome (or the energy to get your primary intermediate activated) is provided by the oxidizer removing hydrogen atoms from the primary intermediate and making it chemically active (grouchy ready to bite). Keep in mind, however, that some of the most useful interactions between hydrogen and oxygen are not covalent but rather weaker interactions known as hydrogen bonds which give water its fluid nature and vital role in life.

As far as the types of melanin, eumelanin and pheomelanin, both start out very similar during their synthesis in the cell. They are both polymers (chains) based on the amino acid tyrosine. Tyrosine is changed through the action of the enzyme “tyrosinase” to a new molecule called dopa, which is then changed by the same enzyme to dopaquinone (Albinos in general lack the enzyme tyrosinase and their cells cannot make melanin).  At this point, eumelanin and pheomelanin go in different directions. Eumelanin chains continue growing by adding derivatives of tyrosine, while pheomelanins add derivatives of both tyrosine and the amine acid cysteine which contains sulfur. These cysteine derivatives form cross links or bridges among themselves which cause pheomelanins to be more tightly packed and resistant to bleach. The switch in the cell to synthesize either type of melanin (by adding tyrosine or adding cysteine) is related to genetic factors. Both types of melanins grow to form large granules of melanin chains wrapped around protein molecules. The chemical structure of both types is quite complex, and both have what is referred to as highly conjugated double bond structure which results in the dark color of the pigment and allows the molecule to absorb UV light and offer protection against harmful radiation. When melanin is oxidized, the conjugated double-bond structure starts to break up and the melanin gradually loses color and becomes “bleached”. It is not eliminated from the hair but remains in the hair in its colorless “bleached” form.

Can cream peroxide developers condition the hair?

Q: Some cream peroxide developers claim to add conditioning to the hair during the coloring process. Is that true? Thank you Dr. Said. Kim, Bellevue, WA

A:  The major role that peroxide plays during the coloring process is to oxidize dye molecules and develop the color. It also lifts some natural color from the hair under higher pH. Most of the chemical ingredients that are added to liquid peroxide to give it a creamy texture are derived from fatty acids. As such, cream peroxide may give the impression of adding conditioning and/or detangling to the hair. However, in order for a product to be considered a conditioner, it should be substantive (i.e. should bind to some degree) to the hair after rinsing. This is not the case with cream peroxide. As soon as it is rinsed off the hair any perception of conditioning is lost. Therefore, simple cream peroxides are not conditioners. Color chemists usually add the conditioning molecules exclusively in the color bottle or tube. After all, the peroxide is rarely used alone.

In general, adding too many ingredients to the developer can also have a diminishing effect on color deposit. In terms of color deposit alone, liquid peroxide is unsurpassed. But many hair-coloring products are designed to work with cream developers for optimal consistency, hold and mixture aesthetics.

Coloring grey hair – Extra ammonia or extra peroxide?

A. Christine, the general rule of thumb is that higher alkalinity (especially in the form of ammonia) results in better color deposit. This is because the higher the alkalinity the more “open” the cuticles become. This is also why demi-permanent colors with lower alkalinity, even if used with high volume peroxide, tend to have less deposit and permanency than the more alkaline permanent colors.

High volume developers tend also to “loosen” the hair structure to some degree and they do that in the presence of alkalinity, acting as mild bleaches. In the case of resistant virgin grey hair, the hair structure is usually strong and the cuticles are well compacted. Ammonia here is generally more effective than peroxide in opening up the hair fiber. However, there comes a point of diminishing returns with both alkalinity and higher volumes of peroxide. Beyond an optimum level, which differs with differing hair types, the damage resulting from the excess of chemicals outweighs their added benefits.

It is always recommended to follow the manufacturer’s instructions of the hair colorant being used since various brands of hair color may have wide ranges of alkalinity. Whatever ‘tweeking’ that may work with one color may cause adverse effects with another. Keep in mind that in most cases you need to adjust neither the ammonia level nor the peroxide volume to achieve good grey coverage. Just make sure the hair is free of metallic deposits such as iron and copper because these metals interfere with color diffusion and deposit inside the hair and make the hair appear resistant to coverage.

Melanin pigments in blond hair

Q. I need to be enlightened on the subject of true blonde hair containing what type of melanin. In the past, I have learned that true blonde hair is composed of dispersed yellow pigments in low concentration.  I have also learned that pheomelanins, which include the yellow and red pigments, do not bleach out while eumelanins (brown pigments) bleach easily. Therefore, how can true blonde hair be bleached out to the palest yellow stage, if it has yellow pigments? Thank you. Barbara, Pasadena, CA.

A. All human hair types at childhood contain the two types of melanin you mentioned. There is no hair type with only one type of melanin. Dark hair has a higher percentage (99%) of the brown pigment, eumelanin, and a much lower percentage (about 1%) of pheomelanin. Blonde hair still has about 95% of eumelanin and about 5% of pheomelanin. Of course dark hair has a much higher overall amount of melanin (eumelanin and pheomelanin) than blond hair.

Let us look at some numerical examples without putting much emphasis on the numbers because they are strictly hypothetical:

If we assume that a dark hair strand has 10,000 “molecules” of total melanin, then by the ratios above, 9900 “molecules” (99%) of these would be eumelanin and 100 “molecules” (1%) would be pheomelanin. In comparison, a blond hair strand of equal size may have only 100 “molecules” of total melanin. Of these, 95 “molecules” are eumelanin (95%) and 5 “molecules” are pheomelanin (5%).

When both dark and blond hair types are bleached, most of the accessible eumelanin in the two types of hair would be broken down and discolored, and only very little of the pheomelanin would do so. The reason why pheomelanin is harder to bleach is because it has sulfur linkages (or ties) that make the molecule more tightly packed and inaccessible to the bleach.

The end result is that dark hair lifts to a brassy undertone because of the significant amount of pheomelanin left behind (let’s say 90 molecules), while blonde hair reaches the palest yellow stage because only very few pheomelanins were there to start with, and they get even less after the bleach (Let’s say 3 or 4 molecules).

So the lesson to keep in mind is that all types of hair have both types of melanin, but the concentrations differ.

Ideal temperature for rinsing chemically-treated hair

Q. Permit me to ask your professional opinion about a situation I have encountered while attending a class on Double Process Blonding.  As I have always rinsed the hair with cool water, I was surprised to learn from this instructor that the opinion had changed and that the water recommendation was now “as warm as the client can tolerate.”  The theory being warm water was more effective in releasing “Quats” from the hair.

I have a double process blonde client that I have had for many years.  Her hair is fine and fragile, but I have always had good success, as I am meticulous about proper application and timing.  After attending this class, I began using much warmer water on her hair.  I also have tried some new bleaches, but always with 20 volume peroxide.  She is experiencing  significant breakage and I am very concerned about this situation.  I would love to know your recommendation on water temperature and if you think this could be the cause of the damage.  I have used many different bleaches on her over the years and have NEVER seen this reaction before. The only thing of significant difference is using very warm, as opposed to cool/cold water.  I have questioned her about nutrition and medication and the only change is she began taking Vitorin about a year ago. I would appreciate your opinion in this matter as I am very concerned about the possible cause.  Any help you could offer would be greatly appreciated. Thank you. Jan, Centennial, CO.

A. Double processing is a very delicate technique which should always be applied with care and expertise. I can judge from your letter Jan, that you are both careful and knowledgeable. I find it surprising that somebody would recommend very warm or hot water to rinse the hair after a chemical service. Very warm water tends to loosen the hair and increase its elasticity, something you would want to avoid when the hair is stressed.

I am also puzzled by the reasoning offered by the instructor to justify the elevated temperature. “Quats” are desirable chemical ingredients that are incorporated into hair care products to condition, detangle and enhance the look of the hair. These are what you add to the hair after a chemical service and I do not understand why you want to rinse them out. Besides, double process blonding does not generate quats in the hair to start with (it would be great if it did). That’s why I think the instructor you mentioned may have had his/her facts mixed up.

My recommendation is that you go back to the rinse technique that you were doing, especially when color is being involved. Please keep in mind however that several factors can contribute to hair breakage. Some of these factors are obvious, such as weathering, combing and curling irons. One unobvious and very important cause is metallic contamination of the hair which can build up over time. Metals such as copper and iron (which can build up on the hair from metallic pipes, well water, and swimming pools) generate free radicals in combination with peroxide and alkalinity. These free radicals can cause severe damage to hair structure and its integrity. It is of utmost importance to make sure the hair is free from metals before you proceed with any chemical service.

Activators and liquid lighteners

Q: Dr. Said, What are liquid lighteners and what are activators. Are they bleaches? Antonio, Santa Rosa, CA.

A:  Liquid lighteners are typically liquid color bases without dyes but with a high load of ammonia or other alkalizing agents. When mixed with liquid or crème peroxide developers, they can generate up to four levels of lift. To enhance their action, a powder activator is usually mixed in. A powder activator is a blend of several ingredients, which can provide an extra source of lifting power in the form of activated oxygen. When you mix a liquid lightener and a peroxide developer alone, activated oxygen is generated as well. But the amount of this active oxygen is limited: A 40-volume developer generates twice as much oxygen as a 20-volume developer and that is why it lifts more (it does not lift twice as much). A 60-volume developer will lift even more than a 40-volume developer because it can deliver more oxygen. But developers higher than 40 volumes are scalp burners and irritators and are rarely used. To provide extra sources of oxygen with less irritation, ingredients identical to what is used in typical bleaches are packaged as “activators”. These powder ingredients are ammonium and/or potassium persulfate that act as additional reservoirs of active oxygen to boost the combined action of the liquid lightener and the developer. That’s why they are also referred to as boosters. The reason they are packaged alone in powder form is that they are (like bleaches) unstable when exposed to moisture, and in an alkaline liquid they start to break down quickly releasing their oxygen in the process. Activators can add one additional level of lift to liquid lighteners. All lighteners whether in liquid or powder form are considered bleaches.

Tube hair color vs. hair color in a bottle

Q. Dr. Said, I hear so many different opinions about color in a tube and color in a bottle. Some say tube color is better because it has calibrated ammonia (whatever that means). Others say color in a bottle gives you better coverage. Please explain to me the difference between the two products and which one is less damaging to the hair. Ryan, Chesterfield, MO.

A. There is absolutely no difference between the two products in terms of the kinds of dyestuff they use. The difference is in the base holding the dyes. Tube colors have higher viscosity cream or gel base than the bottled liquid colors. They are perceived to contain more conditioning ingredients that leave the hair feeling better after the hair coloring service. However, most of the new bottled liquid colors are enhanced with conditioners as well. The real advantage of tube colors lies mainly in their ability to stay put in place and resist dripping especially when processed under heat. Another advantage is that a hairdresser can use half a tube of color and store the rest without fear of color loss due to oxidation. On the other hand, once a bottle of color is opened it must be used within a short period of time or the color gets spoiled because the headspace generated in the bottle after first use will contain enough air to oxidize and deactivate most of the unused color.

Most ammonia-based hair colorants, whether in a tube or in a bottle, have “calibrated” levels of ammonia.  This means that low-numbered shade (darker shades) contain low levels of ammonia because they are designed mostly for deposit. As the shades get lighter (levels 5 through 10) ammonia levels are increased to achieve additional lift that would help in achieving even hair color. High-lift shades (level 10-12) contain the highest level of ammonia.

Whether it is bottle color or tube color, the hair colorist will make the difference between a superb result and an average one. Application, timing, and choice of the right shade can make a huge difference in color deposit and in the condition of the hair. For superior coverage, never be stingy in applying enough color mixture, and never allow the mixture to dry up. The same amount of damage can be generated with the misuse of either tube or bottle color. In reality there is always some degree of damage to hair with any color, but a skilled hair colorist is that who knows how to minimize that damage.

Translucent vs. opaque hair color

Q: I am confused about the terms, opaque and translucent. In the color classes I attended, educators used those terms in describing their line of color. I thought if the color was light it was translucent and as the colors get darker they become more opaque. The educators say “no,” their darker colors are translucent as well. Is that a good thing? Sandra, San Francisco, CA

A: The words translucent and opaque came into existence as descriptive terms with the introduction of demi-permanent hair colororants, as a means to distinguish them from their permanent counterparts. Demi-permanent colors lack the depth of coverage that can be achieved with the permanent ones, and hence they were referred to as translucent, which sounds nicer than saying “incomplete coverage”. But you have every right to be confused because the term “translucent” is used in different contexts, where all it means is “grey blending” as compared to “grey coverage”. Sometimes it is quite desirable to have a “translucent” or “blending” effect on a head of hair especially when the amount of grey hair is less than 10%. Obviously at no time you want to use hair color that deposits an opaque flat paint-like look, because there are several products on the market which deposit natural-looking opaque permanent colors with good reflectance and shine.