• Juan Vilaplana
Living reference work entry


Jewelry as fashion is a field that is continuously evolving; therefore, their composition varies according to fashion and prices.

Jewelers contact with different chemicals depending on the working section: fluxes, mechanical hardening, blanching, stripping, deoxidizing, and alloying.

Currently, the work is done in most hygienic conditions, and the workers are sensitized or irritated less often.

The chemicals most frequently sensitizers are nickel, palladium, cobalt, beryllium, rhodium, gold, and epoxy resins.

The metals currently used are cerium, titanium, tungsten, and tantalum to a lesser extent.


Nickel Cobalt Titanium Steel Silver Mercury Zinc Copper Vanadium Manganese Zirconium Indium 

1 Core Messages

  • Jewelry as fashion is a field that is continuously evolving; therefore, their composition varies according to fashion and prices.

  • Jewelers contact with different chemicals depending on the working section – fluxes, mechanical hardening, blanching, stripping, deoxidizing, and alloying.

  • Currently, the work is done in most hygienic conditions, and the workers are sensitized or irritated less often.

  • The chemicals most frequently sensitizers are nickel, palladium, cobalt, beryllium, rhodium, gold, and epoxy resins.

  • The metals currently used are cerium, titanium, tungsten, and tantalum to a lesser extent.

2 Introduction

The continued increase in the price of noble metals has modified the use and trends in cosmetic jewelry. Currently, the industry tends to multinational companies which, even though using the same chemical elements and similar methods as small industries, due to their economic capacity, work with more advanced technology and with fewer risks for the worker.

Owing to this, and despite the large number of people who work in this sector, we see relatively few patients with occupational dermatitis. Jewelry workers come into contact with different series of chemical substances depending on the section and the industry they work in (Llorente 1989); therefore, we revised different jobs and, for each one of them, made a list of the principal products that are touched. It is our intention to try to make the etiological diagnosis of a possible allergen in context with a determined type of job easier for the reader.

3 Fluxes

Fluxes, also called deoxidizers, purifiers, etc., are the products which make liquidation of the metal easier when it is fluxed; they also avoid oxidation (Pfann 1966). These chemical substances are simultaneously charged with metal, except charcoal, which is added after the metal is fluxed. The principles are outlined in Table 1.
Table 1

Chemicals used as fluxes

Sodium chloride

Powdered glass


Copper chloride


Ammonium chloride

Boric acid

Mercury chloride

Fluor spato


Na and K carbonates

Ammonium fluoride

4 Mechanical Hardening

Once fluxed, all metals show as large crystals under the microscope. Using mechanical treatments such as rolling, bending, sheeting, and drawing, these crystals become smaller and smaller, and at the same time, the hardness of the metal increases. This increase in hardness is called “mechanical hardening,” which has a maximum point at which the metal breaks when worked, leaving no other possibility than to return the crystals to their original size to be able to continue working with the metal mechanically; this treatment is known as “annealing.”

Annealing consists of heating a metal or alloy to a determined temperature and then cooling it with water, air, or charcoal or in a controlled atmosphere. During this process the operators do not touch any product that merits special consideration (Michaelson 1988).

5 Blanching, Stripping, or Deoxidation

The blanching, stripping, and deoxidation solutions are used to eliminate oxides from the metals, such as the remains of smelters, borax, colophony, mercuric chloride, and other components outlined in Table 1. The substances used more often in this process are described in Table 2.
Table 2

Chemicals used as antioxidants

Tap water


Sulfuric acid

Sodium cyanide

Chlorhydric acid


Nitric acid

Ammonium persulfate

Sodium dichromate

Ferric sulfate

Potasic alumbre


Potasic nitrate


6 Alloys

Metals are never worked in their “pure” state for two reasons: the first is that chemically pure metals do not exist, and even though they are in millions of parts, they have some contaminant; the second reason is that the most pure metals are not always those that offer the best mechanical or chemical properties, owing to which the great majority of pieces are alloys that, in many cases, contain various metals (Touloukian and Ho 1981).

When metals are alloyed, their properties always change (Shaefer et al. 1977), and in the field of jewelry, it is mainly an attempt to lower costs by adding cheaper metals which also have the desired physical-chemical properties. Alloys tend to take the name of the metal they contain in the highest quantity. Therefore, “nickel silver,” “brass,” and “bronze” are the so-called alloys of “copper” as this is the most abundant metal they contain. There are thousands of alloys on the market, and in this chapter, we shall only comment on some “types” that constitute the basis of a number of studies of jewelry and costume jewelry. Details of these types are given in Table 3.
Table 3

Metals in different alloys

Primary metal in the alloy

Other metals that may be part of this alloy


Copper, nickel, palladium, silver, zinc, iron, cadmium, chromium, and aluminum


Copper, indium, ruthenium, gallium, zinc, cobalt, iridium, and gold


Copper, zinc, nickel, brass, and alpaca; depending on the color and properties desired


Nickel, copper, silver gallium, and gold

Tungsten carbide

Wolframium, nickel, iron, copper, cobalt, molybdenum, and chromium

Stainless steel

Chromium, nickel, manganese, aluminum, molybdenum, titanium, niobium, and tantalum


Aluminum and vanadium

Currently, multiple alloys, such as indium, tin, antimony, etc., are being tested to avoid the easy oxidation of silver (Bever 1986; Lida and Guthrie 1988). These formulas are varied depending on what they are to be used for and the characteristics and final price desired. We have given a small orientation basically referring to the materials used, and thus we talk about:
  • Gold alloys which may contain copper, nickel, palladium, silver, zinc, iron, cadmium, chromium, and aluminum.

  • Platinum alloys which may contain, besides copper, indium, ruthenium, gallium, zinc, cobalt, and gold.

  • Silver alloys which are composed by copper, zinc, nickel, brass, or alpaca, depending on the color and properties desired.

  • Palladium alloys which may contain nickel, copper, silver gallium, and gold.

In addition to these metals, we also find rhodium which is used to coat the pieces.

7 Soldering

Soldering is the union of two pieces of metal using another metal or alloy at the lowest fusion point of the part to be soldered. Sometimes, the metal used is exactly the same as the parts to be soldered, and this is called autogenous soldering (Bever 1986).

Solders can be divided into two groups: (1) soft solder with low fusion point and (2) hard or high-fusion-point solders. With either process, the metals used should be as pure as possible, and if possible, they should be obtained through electrolytic methods. The low-fusion-point or soft solders are not used much for soldering precious metals, as they contain lead and tin and these can contaminate; however, they do have the advantage of a very low fusion point (between 940 and 2920 °C). Other metals that can make up the composition of the solders are silver, antimony, cadmium, and zinc.

The hard solders are completely different from the above mentioned and are classified as:
  1. 1.

    Copper alloys for soldering. These also contain zinc, nickel, tin, and lead.

  2. 2.

    Silver alloys for soldering. Besides silver, these also contain cadmium, copper, zinc, brass, and tin.

  3. 3.

    Alloys for soldering colored gold. It is important that these alloys contain the same concentration of gold as the piece to be soldered, with the appropriate composition, for the fusion point to be as low as possible. Therefore, there is the already mentioned silver, copper, zinc, and brass at different concentrations, as well as gold in their composition.

  4. 4.

    Alloys for soldering white gold. These alloys must have the same percentage and same quality of white gold as the piece to be soldered. These alloys may also contain silver, nickel, cadmium, zinc, copper, brass, and nickel silver. Last year, Metalor patented a method (0686136 A5 CH92-2563920817) for soldering white gold which does not contain nickel and, therefore, should not produce problems of contact dermatitis. Gold, manganese, zinc, gallium, indium, copper, and silver are included in its composition.

  5. 5.

    Alloys for soldering platinum. The high fusion point of platinum means that almost any alloy can be used as, in the majority, the fusion point is much lower. The materials used most are mixtures of platinum, gold, silver, and copper. A final rhodium bath is used to hide the small defects that may remain in the alloys to be used to solder white gold. At present, a Neodimio YAG laser is used for all types of soldering; this allows soldering gold with a purity of 98% and, of course, any metal or alloy even though it has a high fusion point. The patent of Schone Edelmetaal BV has recently been introduced in this field; this is used to solder precious metals and does not contain cadmium, thereby avoiding possible toxic smoke. Moreover, it does not contain nickel and therefore avoids possible allergic reactions. The composition is silver (0–33%), copper (85–30%), zinc (0–10%), indium (0.5–8%), tin (8%), and the remainder is gold.


8 Casting

Two methods are used to obtain casts used for later mass production: (1) wax casting and (2) vulcanized rubber casts. The casts used in jewelry and costume jewelry are almost always made from steel, although copper, zinc, aluminum, and tin-bismuth casts are also used.

9 Baths

Prior to degreasing the pieces with trichloroethylene, toluene, benzene, and detergents, they may have to be placed in a bath before their definite finishing by polishing. These baths consist of applying a metal over another metal or cast which it covers. The technique used most often is the galvanotechnique, and the materials used are gold, rhodium, nickel, copper, brass, silver, and tin, although more recent techniques allow the use of any type of metal, including plastics and resins. Tin electrolysis with hydroxyphenyl-sulfone (DDS), dimethylmethane, and naphtosulfonic acid (Weast 1989) is used for costume jewelry.

10 Lacquers, Varnishes, and Enamels

Lacquering or varnishing consists of covering the finished objects with a layer of plastic material. Two decades ago, nitrocellulose was used. Nowadays, modern electrolytic systems are used to deposit plastic material that becomes transparent at high temperatures. The resins used are polyurethane, vinyl, acrylics, and epoxy. We also should take into account chrome, nickel, cobalt, and various metallic oxides which can be found in enamels (Motolese et al. 1993).

11 Recuperation of Precious Metals

In making a piece of jewelry, precious metal is fluxed, annealed, sawn, filed, and ground or honed, which produces a loss called reductions. These reductions have become less with the automation of the industry; however, the price of metals has increased, and recuperation of the metals lost by “reductions” continues. Burning or calcination, grinding, magnetization, acid treatment, fusion, and electrolysis are all used in this recuperation. The workshops that do not work on precious metals do not usually gather these “reductions.”

Due to the vastness of this subject, we will not enter into more detail about the work possibilities of this sector. We only want to provide the doctor, who has to make the diagnosis and treat the patients who work in this area, with more knowledge about which materials the workers touch most frequently and the consequent etiological possibilities.

12 Clinical Manifestations

The dermatological clinical manifestations are multiple and not always directly related to work. An example repeated with a certain frequency is women who begin to work in this area who are already allergic to costume jewelry; recent studies carried out in our department of dermatology have shown that 19.5% of women between 18 and 60 years of age do not tolerate costume jewelry, and of that 19.5%, only 2% have carried out a patch test to find out the exact etiology. This is very important; these patients should be studied before beginning this type of work and should only be employed in sections where they will not touch the materials to which they are sensitive (Kraus and Muselinovic 1991; Milkovic-Kraus and Macan 1996).

The sensitive area always appears on the uncovered areas, basically the hands, and depending on the causal agent and the form of handling, the dorsum (polishing powder), palms (picking pieces while still wet), and fingertips (picking up the piece to solder) may also be affected. The subjective symptom of pruritus is constant with variable intensity, sometimes to the point that intense lesions from scratching hide the basic clinical picture, which has the following manifestations.

12.1 Dry and Fissured Dermatitis of the Hands

Dry hands syndrome is seen more frequently in atopic patients who touch strong acids (sulfuric, hydrochloric, nitric, etc.) (Kiec-Swierczynska 1987) without due protection and who present a pruritic xerosis on the palms and interdigital areas during the more active periods. If the evolution continues, it can liquefy and fissure principally on the articular areas. This pathology is more frequent in women and it is worsened by housework. On two occasions, the sensibility was shared with cobalt, with which they had contact in both jobs (Vilaplana et al. 1987).

The dorsum of the hands can be affected in some patients, above all when they manipulate liquids or work on polishers. Possible erythematous, papulous, and even frankly eczematous lesions may be present, worsened by intense itching which is a habitual accompanying symptom. In some industries, the soaps used for washing hands are very aggressive and clearly contribute to this pathology (Kiec-Swierczynska 1987). High indexes of dry and fissured dermatitis of the hands were observed in two industries; more than 90% of cases improved within a period of 2 months of changing from the habitual soap – a basis of lauryl sodium sulfate with crushed almond shell to favor cleaning – to a wheat germ soap, with disodium cocoyl glutamate as surfactant, and later hydration with a wheat germ cream.

12.2 Dyshidrosis

Dyshidrosis manifests as small, very pruriginous interdigital vesicles, frequently modified by intense scratching, and these appear during periods of greater perspiration. In our country, a high percentage of patients (85%) are atopic without always being able to relate the symptoms to a determined allergen, although with a certain frequency (22%) they are nickel positive (Roduner et al. 1987; Yokozeky et al. 1992). Even though the patients are not always in contact with this metal at their work, it is so ubiquitous that we cannot assure its etiological role.

Another group of patients relate their dyshidrosis directly to the use of rubber gloves, without any existing positive patch test to any of the rubber allergens. These cases are due to perspiration and occlusion in the interdigital area. To our understanding, this pathology reacts to several stimuli, such as allergens, irritant substances, and occlusion. It is seen more frequently during hot seasons. In the last 15 years, we have quite often seen patients sensitive to cobalt who present with outbreaks of dyshidrosis which, in only a few cases, clearly improve on ceasing contact with cobalt in the industry. We believe that this metal is also ubiquitous and is contained in many products for domestic use.

12.3 Irritative Pulpitis

Irritative pulpitis is a frequent problem in workers. It is provoked by contact with the abrasive surface of some pieces during the period of fabrication and contact with strong acids that remain on the surface of the pieces after rust removal and blanching, which are not sufficiently dry.

12.4 Allergic Contact Dermatitis

In the majority of cases, we have observed allergic contact dermatitis to occur on the hands, with the exception of two cases: a patient with nickel scabies and a patient who presented a toxic dermatitis on being treated with injectable thiomalate gold sodium (Miocrin). This patient already knew of her sensitivity to jewelry and costume jewelry, although no patch test had been carried out.

On two occasions, we have studied patients with a possible airborne contact dermatitis, which affected uncovered areas (face, forearms, and hands); one of these patients worked in the finishing of rings (polishing, milling, lacquering, varnishing), and another patient worked with nickel and chrome electrolytic baths. Both gave negative results to patch tests and it was thus considered as an irritative dermatitis. The clinical picture depends on when we see the patient and whether we can see erythematous, papulous, vesiculous, exudative, crusted, scaly, or liquefied eczema (Garner 2004).

We have had two patients with a more localized clinical picture – eczematous and fissured pulpitis – who worked with methacrylates in the finishing of earrings in costume jewelry. Likewise, we have seen three cases of sensitization to antioxidants in rubber gloves in persons not considered as patients; they wore rubber gloves to do housework.

In the last 13 years, we have studied 180 patients who worked in the production of jewelry, costume jewelry, and prosthesis. All of them have been patch-tested using the following series:
  1. 1.

    Special metal series (Table 4)

  2. 2.
    Chemotechnique standard series, which also contains nickel, chrome, cobalt, antioxidants and rubber accelerants, colophony, and epoxy resins
    Table 4

    Special metal series


    Zinc 2.5 pet


    Mercury 0.5 pet


    Mercuric chloride 0.1 pet


    Aluminum chloride hexahydrate 2.0 pet


    Mercury ammonium chloride 1.0 pet


    Aluminum 100 pet


    Palladium chloride 2.0 pet


    Gold sodium thiosulfate 2.0 pet


    Copper sulfate 2.0 pet


    Gold sodium thiosulfate 0.5 pet


    Copper oxide 5.0 pet


    Tin 50.0 pet


    Iridium (III) chloride trihydrate 1.0 pet


    Iridium 1.0 pet


    Indium 1.0 pet


    Titanium nitride 5.0 pet


    Titanium oxide 10.0 pet


    Zinc chloride 2.0 pet


    Titanium oxalate 5.0 pet


    Calcium titanate 10.0 pet


    Titanium 10.0 pet


    Vanadium 5.0 pet


    Molybdenum 5.0 pet


    Vanadium (III) chloride 1.0 pet


    Manganese (II) chloride 2.0 pet


    Stannous oxalate 1.0 pet


    Zirconium chloride 1.0 pet


    Tungsten (Wolfram) 5.0 pet


    Iron (III) chloride 2.0 pet


    Phenyl mercuric acetate 0.01 aq


    Potassium dicyanoaurate 0.1 aq


    Silver nitrate 1.0 aq


    Cadmium chloride 1.0 aq


    Ammonium hexachloroiridate 0.1 aq


    Indium (III) chloride 10.0 aq


    Lead acetate trihydrate 0.5 aq


    Indium sulfate 10.0 aq


    Ammonium molybdate tetrahydrate 1.0 aq


    Stannous chloride 1.0 pet


    Lead chloride 0.2 aq


    Ammonium hexachloroplatinate 0.1 aq


    Ammonium tetrachloroplatinate 0.25 aq

We have systematically added the allergens listed in (Table 5) to these series
Table 5

Substances added to study these patients


Saturated aqueous solution


1% pet


1% pet


1% pet

Methyl methacrylate

2% pet

Ethyleneglycol dimethacrylate

2% pet

Arsenate sodium

1% aq. sol.


10% pet

Mercury chloride

0.5% pet

Ammonium fluoride

2% pet

Ammonium persulfate

2% pet

From the study of 180 patients, we have found that 80 patients gave a negative result to the patch test; 100 patients gave one or more positivities. In order of frequency, these were as follows:
  • Nickel. Seventy-eight patients were positive, and of them, 22 also presented positivity to palladium, 20 were cobalt positive, 5 were rhodium positive, 5 were beryllium positive, and 1 was vanadium positive.

  • Palladium. Thirty-nine patients were patch-test positive; of them, 27 were also positive to nickel, 1 to vanadium, another to epoxy resin, and 3 to cobalt.

  • Cobalt. Twenty-five patients were patch-test positive, and the following associations were found: 15 were also nickel positive, and 2 were rhodium positive, and 1 was positive to epoxy resin.

  • Beryllium. Fourteen patients showed positivity to this metal, four also with nickel and two with cobalt. We should point out that in one patient the positive patch to beryllium lasted 4 months.

  • Rhodium. Four patients were positive, three were also nickel positive, and two was also positive to cobalt.

  • Vanadium. Three patients were positive, one also to nickel and the other to palladium.

  • Gold. Nine patients were positive, two also to platinum.

  • Platinum. Two patients were positive and also showed positivity to gold.

  • Mercury. Six patients were positive; only one of them was directly related to work.

  • Epoxy resin. Seven patients were positive; one was positive to cobalt and one to palladium.

  • Methyl methacrylate. Five patients were positive; they demonstrated unique positivity and relevance to their work of plating earrings with this substance.

  • Thiourea. One patient was positive.

  • Ammonium persulfate. One patient was positive.

We do not mention allergens that form a part of other series and have given positive reactions with no relationship to work (neomycin, cam mix, wool alcohols, etc.).

From our study, and given the frequent multiple sensitizations, we deduct that sensitization is more frequent in women who present positivity to nickel and who are later sensitized to other metals. We agree that cross-reactions exist among some of them (Kränke and Aberer 1996) and believe that the greater use of metals, such as palladium, has contributed to the alarming increase in sensitivities. There are authors who affirm that this metal is even more sensitizing than nickel (Wahlberg and Boman 1992).

12.5 Granulomas Caused by Metals

There are various metals that can produce granulomas (Jones Williams 1971) (mercury, chrome, zirconium, cobalt, aluminum (Rublin 1956), and beryllium). The most frequent granulomatous reactions occurring with this type of work are those produced by cobalt and beryllium; however, it is necessary to keep in mind that aluminum and zirconium contained in deodorants can also produce this clinical picture.

12.6 Hyperpigmentations for Incrustation of Different Metallic Salts on the Skin

In our understanding, hyperpigmentation is only a tattoo provoked by the penetration of different metallic salts (copper, cobalt, aluminum, gold, tin, iron, zinc, and, above all, silver) during the process of polishing and milling. Normally, only the dorsum of the hands and forearms are affected and very rarely the face and other uncovered areas (Fisher 1971).

12.7 Folliculitis and Furunculosis

There are various metals that can produce contact folliculitis; those we have seen most frequently are cadmium, vanadium, antimony, and copper. We have not had the opportunity to see any furunculosis caused by arsenic, even though it has been described in the literature (Holinquist 1951).

13 Prophylaxis

Currently, the industries in this field have greatly improved both dermatological and respiratory protection, and some factories look more like an operating theater than previously when there was dust and dirt on the floor and the majority of operations were carried out manually. A spectacular labor improvement has been the change experimented in the baths and galvanotechnique operations, which are now carried out in completely sealed containers and automated. We believe that adequate protection of the hands when touching irritative products, frequent handwashing with nonirritant soaps, and the use of hydrating creams with a certain frequency, above all in atopic people, would be enough to reduce the dermatological problems in this sector.

14 The Future

In a few industries like this one, the future is today. We have reviewed the latest advances in jewelry alloys and have been surprised that, over the last few years, a series of “non-allergic” products have been patented, based on the fact that they do not contain nickel, and of these the following have already been commercialized in various countries:
  1. 1.

    Patent JP 09053159 A970221 (9718): Cr (20–26%), Mo (2–2.5%), Ti (0.4–0.8%), Nb (0.5%), V (1%), Zr (0 5%), and Fe.

  2. 2.

    Patent EP 64r868 Al 950308 (9514): EN which contains C, N, Si, W, Mo, V, Y, Nb, li, Al, S, Se, Ie, Zr, Ca, Pb, and Ag.

  3. 3.

    Patent Al 9201393 A931215 (9405) which contain the following elements in their composition: C, S, Mn, Cr, Mo, N, V, Nb, la, W, Al, Ii, Cu, B, and Fe.

  4. 4.

    US Pat. No. 9,289,037 (Serinium) will make it easier to manufacture materials based on cobalt, chromium, aluminum, titanium, etc. This will make it much harder, stainless, nontoxic, and hypoallergenic.


There are many new interesting advances in men jewelry such as pieces made of titanium, stainless steel, and tungsten carbide with addition of tantalum and niobium. Cerium, a magnetic rare-earth metal, is today used in aluminum alloys.

Other new alternative for platinum jewelry is an alloy with hafnium and molybdenum, with fewer quantities of tantalum, wolframium, vanadium, zirconium, and titanium.

A new alloy named Platinum Sterling, composed of fine silver with a modifier of platinum unit (4%/6%) and a small amount of copper (1%), is acquiring patent process.

These compositions and many others that have appeared during recent months with the qualification “nickel-free” and “non-allergic” support our idea of having a metal series as extensive as possible (Table 4). Finally, and due to the large amount of material that these patients could have had contact with, a list of substances with irritative capacity is provided in Table 5, and in Table 6 we can see the list of substances that, to our judgment, shows more capacity to produce allergic contact dermatitis (Table 7).
Table 6

Substances with irritative capacity

Boric acid

Powdered glass

Ammonium chloride

Ammonium fluoride


Cadmium chloride

Vanadium chloride

Sulfuric acid

Nitric acid

Sodium dichromate

Sodium cyanide


Naphtosulfonic acid

Sodium lauryl sulfate aluminum


Fluor spato

Table 7

Substances with allergenic capacity









Mercury metal

Epoxy resin

Methyl methacrylate


Ammonium persulfate

Potassium dichromate


Thiuram mix

Mercapto mix

Nowadays, the use of industrial adhesives is increasing rapidly in many types of applications, constituting a great revolution of the traditional methods to fix, unite.

The commonly used processes such as welding and riveting are being replaced by these joining processes, improving their performance and mechanical performance.

Epoxy paste adhesives are resistant to depression (does not flow) during curing and modified epoxy adhesive designed for sealing/bonding and encapsulation applications.

At present, the production of jewelry and imitation jewelry has begun in 3D printing; With this method, you can already manufacture.

Using 10 different 3D printing technologies, 20 different materials, and over 100 possible colors and finishing combinations, this method can offer the highest quality and turn your ideas into 3D-printed reality.

From Titanium to Rubber-like, Multicolor, Polyamide, 18K Gold, titanium, Steel, silver, brass, bronze, copper, aluminum and more the highest quality to turn your ideas into 3D-printed reality.

As for the advantages of manufacturing 3D printed jewelry, among them is the possibility of using digital media for its design and production. On the other hand, the weakness of this method affects the realization of functional jewelry, since finding a way to get practical models is a challenge. Even so, it is an important experimental field on the rise, as it is increasingly common to find jewelry items that have incorporated 3D printing in some part of their process.


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Copyright information

© Springer International Publishing AG, part of Springer Nature 2018

Authors and Affiliations

  1. 1.BarcelonaSpain

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