Aluminized steels are steels that have been hot-dip coated with pure aluminum or aluminum-silicon alloys. This hot-dip coating process is termed hot-dip aluminizing (HAD)...
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This article gives comprehensive insights into Titanium Metal and its alloys.
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Titanium metal, with the symbol Ti, is the ninth most abundant element in the earth‘s crust. It does not occur in large deposits, yet small amounts of titanium are found in almost every rock. Titanium is a shiny grey metal with a low corrosion rate and high strength; it is used for various applications. It was discovered by William Gregor, an English chemist and mineralogist, in 1791; he thought it was a compound. In 1795, he realized it was an independent element. Later, it was named by Martin Heinrich Klaproth, a German chemist, after the Titans of Greek Mythology.
Titanium is placed in D-Block in the periodic table as the first element. It is classified as a transition metal with atomic number 22, which means it has 22 electrons and 22 protons; it has an atomic weight of 47.867 Daltons. Titanium belongs to period 4 and group 4 of the periodic table because of its electronic configuration. The last two electrons of titanium metal reside in the fourth orbital, making the configuration 1s2 2s2 2p6 3s2 3p6 3d2 4s2. This electronic configuration explains the chemical bonds of the element and some other properties.
Titanium constitutes 0.44 percent of the earth‘s crust, and it is widely distributed. Ninety percent (90%) of the titanium occurs in the form of ilmenite minerals in the earth's crust. Ilmenite minerals are compounds of iron, titanium, and oxygen called iron titanium oxide with the symbol FeTiO3. The remaining amount of titanium is found in the form of anatase, perovskite, rutile, leucoxene, sphene, and other minerals. These minerals are found in the form of compounds in sand, rocks, soils, and clays. It can also be found elsewhere in nature: in plants, natural waters, animals, stars, and meteorites.
Titanium metal is known to have five stable isotopes. These include titanium-46, titanium-47, titanium-48, titanium-49, and titanium-50. The most abundant isotope of titanium metal is titanium-48 with 73.8% natural abundance, but there are numerous radioisotopes of titanium. Today, 21 radioisotopes of titanium metal are known; the most stable are titanium-44, titanium-45, titanium-51, and titanium-52. All four stable radioisotopes have a different half-life. The half-life of titanium-44 is 63 years, titanium-45 has a half-life of 184.8 minutes, titanium-51 has a half-life of 5.76 minutes, and titanium-52 has a half-life of 1.7 minutes.
Titanium metal is considered to have superior physical properties. It is considered to be an element that is physiologically inert. It has a high strength-to-weight ratio, which makes it an ideal candidate in an application where lightweight yet strong materials are essential, for example, joint replacement and dental implants. It is a very strong metal that has a low density of 4.5 g/cm3 with high melting and boiling points. The melting point of titanium metal is more than 1650 ˚C or 3000 ˚F. The boiling point of titanium is 3287 ˚C. High melting and boiling points make titanium a very useful metal in terms of refractory properties. It is also a ductile metal, especially when in an oxygen-free environment. Its lustrous grey-whitish appearance also makes it useful for coating metal or for displaying. Additionally, titanium dioxide in pure form is practically clear, with a high refractive index, which creates high optical dispersion—higher than that of a diamond. Titanium has a fairly low thermal and electrical conductivity when compared to other metals although it exhibits superconducting properties when it is cooled below 0.49 K temperature, which is its critical temperature. When titanium in its elemental form is bombarded with deuterons it can become highly radioactive.
Pure titanium is almost 99.2% pure and is a lustrous metal with low density and high corrosion resistance. It is even resistant to strong liquids such as sulfuric acid, moist chlorine gas, chloride solutions, hydrochloric acid, and most organic acids. However, it can burn in the air and stands out as the only element that would burn in the presence of nitrogen gas. Titanium is considered to be a strong metal with an ultimate tensile strength of 434 MPa that makes 63,000 psi which is roughly equal to the strength of a low-grade steel alloy. This means titanium can be used as a replacement for steel—a major benefit, as it is 45% lighter than steel. It is twice as strong as aluminum and 60% denser. This is why the most commonly used alloy is 6061`-T6 aluminum alloy. When titanium is mixed with other metals, the alloys can reach a tensile strength of more than 1,400 MPa, which makes 200,000 psi. However, titanium can lose its strength at temperatures greater than 430˚C because it is not as hard as high grades of steel. Titanium is a dimorphic element with a hexagonal form that slowly converts into a body-centered cube at an elevated temperature of 880 ˚C. This happens because the specific heat starts to increase dramatically as the transition temperature of 880 ˚C is reached. However, when the element is in cubic β form, the specific heat becomes constant.
The chemical behavior of titanium metal shows significant similarities with that of zirconium and silica. Titanium, zirconium, and silica all belong to the first transition group in the periodic table. Titanium resides in group 4 (IVB) of the periodic table, which means it is in the middle. The arrangement of elements in the periodic chart shows how the elements are related to one another chemically. As it is in the middle of the table, we know titanium exhibits properties between those of metals and non-metals. For example, just like magnesium and aluminum, titanium metal and its alloys immediately oxidize whenever exposed to the air. Titanium rapidly starts to react with oxygen molecules at around 1,200 ˚C, and it can exhibit the same behavior at a reduced temperature of 610 ˚C when the oxygen is in pure form. Each reaction produces titanium dioxide. Titanium behaves as an inert element in the presence of oxygen and water, which means it does not react with oxygen and water at ambient temperature conditions. The reason for such behavior is titanium tends to create a passive oxide coating, which behaves as a protector for the material to oxidize further. This protective layer can be as thin as 1 – 2 nm and as thick as 25 nm. It depends upon the period of time the bulk metal is exposed to oxygen. It takes almost four years to create a 25nm thick layer.
This protective layer enables titanium to become an excellent corrosion-resistant element—almost as effective as platinum. This property makes it resistant to even strong liquids such as sulfuric acid, moist chlorine gas, chloride solutions, hydrochloric acid, and most organic acids. However, it can be corroded when exposed to concentrated acids. Thermodynamically, titanium is a very reactive metal due to its negative redox potential, and it burns in the atmosphere at a temperature lower than its melting point. It can react with chlorine at 550 ˚C and can also combine with other halogen gases although it absorbs hydrogen. The melting of titanium can only occur in a chemically inert atmosphere such as a vacuum. Titanium's thermodynamic properties do not allow it to melt in normal conditions, because it becomes more reactive at elevated temperatures and can catch fire if the oxygen molecules are present in its environment. However, as mentioned before, titanium is quite unreactive in general.
Titanium is a transition metal that also exhibits similarities in its chemical behavior, especially in lower oxidation states, to that of chrome and vanadium. It has various oxidation states, including 4+, 3+, and 2+. However, the oxidation state 4+ is the most stable. Titanium oxide ore reduces with water vapors and forms dioxides and hydrogen. It reacts in the same manner with hot concentrated acids—with a minor difference. When reacting to hot concentrated acids, it creates chlorhydric acid and trichlorides.
The chemical properties chart of titanium is given in Table - 2
Titanium chemistry is dominated by the titanium oxidation state +4 because it is the most stable state in which titanium occurs. However, the +3-oxidation state of titanium compounds is also common. Naturally, titanium complexes have an octahedral coordination geometry, but one notable exception here is TiCl4. This compound is called titanium tetrachloride, and it has a tetrahedral geometry. This geometry is due to the high oxidation state of the titanium tetrachloride, which results in a higher degree of covalent bond. In the transition metal only, titanium is known to form aqua Ti (IV) complexes: water ligand titanium ion complexes.
The term titanates indicates the titanium (IV) compounds: the titanium tetra(element) compounds, such as TiCl4, the titanium tetrachloride, and BaTiO3, barium titanate. These compounds are known for their piezoelectric properties and serve well in the interconversion of sound and electricity as transducers. The mineral in which titanium is found in the most abundance, ilmenite, is also a titanate. Ilmenite is a FeTiO3 compound. Stars, rubies, and sapphires also have titanium dioxide TiO2 properties of asterism. This is the reason they have star-forming shine. The most important oxide of all titanium oxides is TiO2; titanium dioxide occurs in three different polymorphous states: rutile, anatase, and brookite. All three polymorphous states are white di-magnetic solids.
There are numerous titanium suboxides known today. The reduced stoichiometries of titanium dioxide are attained by the spraying of atmospheric plasma. The titanium (III, IV) oxide, Ti3O5 is a purple-colored semiconductor that is obtained from the reduction process of Titanium dioxide TiO2 in the presence of hydrogen gas at elevated temperatures. The titanium (III, IV) oxide is an ideal compound to vapor-coat surfaces with titanium oxide for corrosion resistance and aesthetic purposes.
The alkoxides of titanium are obtained by reacting titanium tetrachloride with alcohols. These are ideally used for depositing solid titanium dioxides with the help of the sol-gel process in industries. Additionally, titanium iso-prop-oxide is used in the preparation of chiral organic compounds with the help of the Sharpless epoxidation process. Titanium also has a variety of sulfite compounds. However, titanium disulfide is the only titanium sulfide regularly used. It has a layered structure and serves as a cathode in the manufacturing of lithium-ion batteries.
Titanium nitrides and carbides are members of the refractory transition family. The nitrides of titanium have properties of both covalent compounds. They exhibit extreme hardness, high melting and boiling points, thermodynamic stability, and high thermal and electrical conductivity. Titanium nitride, TiN, has a hardness of 9.0 on the Mohs scale, which is the same hardness as sapphire and carborundum. Because of this extreme hardness property, it is used as a coating material for cutting tools; for example, drill bits are coated with titanium nitride and carbides. It is also used for coating for aesthetic purposes because it gives a shiny gold-colored finish. It also serves as a barrier material in the fabrication of semiconductors.
The most common halide of titanium is titanium tetrachloride, TiCl4, which is a colorless and volatile liquid. The industrial titanium tetrachloride is yellowish and tends to hydrolyze in the air with spectacular emission of white-colored clouds. Titanium tetrachloride is also used in the extraction of titanium metal from its ores. This process is called the Kroll process. Additionally, it serves to obtain titanium dioxide, which is used in white-colored paints. Titanium halides are widely used as a Lewis acid. Titanium tetraiodide, TiI4, another halide of titanium, is obtained from the Van Arkel process as high purity titanium metal. Titanium (III) and titanium (II) can also form stable halides. An important example is titanium trichloride and titanium dichloride. These compounds are used as a catalyst in the production of polyolefins. They also serve as reducing agents in organic chemistry.
The most commonly known organometallic compound of titanium is titanocene-dichloride, (C5H5)2TiCl2. The titanium organometallic complexes are studied intensively for polymerization catalysts. Other organometallic complexes of titanium include Petasis reagent and Tebbe‘s reagent.
Titanium in its pure form comes in various grades that are suitable for specific applications. Titanium CP4, aka Grade – 1, is the softest grade with the highest ductility, toughness, and corrosion resistance. Due to its cold forming characteristics and brilliant welding properties, it is popular in the architecture, automotive, medical, and processing industries. This grade is available in the form of bars, flanges, sheets, welding wires, and forgings.
Another grade that has excellent cold forming properties with corrosion resistance and welding properties is CP3 – Grade 2. It is used in aerospace, automotive chemical architecture, marine, and medical industries.
CP2 – Grade 3 is considered to be stronger than previous grades.
CP1-Grade 4 titanium is the strongest and most corrosion resistant but has lower ductility. It is commonly used in medical and aerospace applications.
Grade 7 titanium has the best mechanical and physical properties with excellent fabrication and welding properties. It is even corrosion-resistant to reducing acids.
Grade 11 - CP Ti-0.15Pd has similar properties to Grade 2.
The following tables indicate the available standards & forms of pure titanium grades.
|S. No.||Grade||Standards||Available Forms|
|1||CP4 – Grade 1||ASME SB-363, ASME SB-381, ASME SB-337, ASME SB-338, ASME SB-348, ASTM F-67, ASME SB-265, ASME SB-337, ASME SB-338||Bars, Flanges, Sheets, Welding Wires, and Forgings|
|2||CP3 – Grade 2||ASME SB-363, ASME SB-381, ASME SB-337, ASME SB-338, ASME SB-348, ASTM F-67, AMS 4921, ASME SB-265, AMS 4902, ASME SB-337, ASME SB-338, AMS 4942||Bar, Fittings, Flanges, Forgings, Pipe, Plate, Sheet, Tube, Welding Wire, Wire|
|3||CP2 – Grade 3||ASME SB-363, ASME SB-381, ASME SB-337, ASME SB-338, ASME SB-348, ASTM F-67, AMS 4921, ASME SB-265, AMS 4902, ASME SB-337, ASME SB-338, AMS 4942||Bar, Fittings, Flanges, Forgings, Pipe, Plate, Sheet, Tube, Welding Wire, Wire|
|4||CP1 – Grade 4||ASME SB-363, ASME SB-381, ASME SB-337, ASME SB-348, ASTM F-67, AMS 4921, ASME SB-265, AMS 4901, ASME SB-338||Bar, Forgings, Sheet, Welding Wire, Wire|
|5||Grade 7||ASME SB-363, ASME SB-381, ASME SB-337, ASME SB-338, ASME SB-348, ASME SB-265, ASME SB-337, ASME SB-338||Bar, Forgings, Plate, Sheet, Tube, Welding Wire, Wire|
|6||Grade 11 – CP Ti-0.15Pd||ASME SB-338||Tube|
The following tables indicate the available standards of titanium grades.
|S. No.||Grade||Standards||Available Forms|
|1||Grade 5 – Titanium 6Al-4V||ASME SB-265, AMS 4911, ASME SB-348, AMS 4928, AMS 4965, AMS 4967||Various|
|2||Grade 6 – Titanium 5Al-2.5Sn||ASME SB-381, AMS 4966, MIL-T-9046, MIL-T-9047, ASME SB-348, AMS 4976, AMS 4956, ASME SB-265, AMS 4910, AMS 4926||Bar, Forgings Plate, Sheet, Wire|
|3||Grade 9 – Titanium 3Al-2.5V||AMS 4943, AMS 4944, ASME SB-338||Bar, Forgings Plate, Sheet, Wire|
|4||Grade 12 – Ti-0.3-Mo-0.8Ni||ASME SB-338||Tube|
|5||Grade 19 – Titanium Beta C||MIL-T-9046, MIL-T-9047, ASME SB-348, AMS 4957, AMS 4958, ASME SB-265||Various|
|6||Grade 23 – Titanium 6Al-4V ELI||AMS 4911, AMS 4928, AMS 4930, AMS 4931, AMS 4935, AMS 4965, AMS 4967, AMS 4985, AMS 4991, MIL -T-9046, MIL -T-9047, BSTA 10,11,12, BSTA 28,56,59, DIN 3.7165, AMS 4907 ELI, AMS 4930 ELI, AMS 4956 ELI, ASTM F136 ELI, UNS R56407||Bar, Forgings, Plate, Sheet, Welding Wire, Wire|
|7||6Al-6V-2Sn – Titanium 6-6-2||AMS 4919, AMS 4952, AMS 4975, DIN 3.7164, GE B50 TF22, GE B50TF21, GE B50TF22, GE C50TF7, MIL F-83142, MIL T-9046, MIL T-9047, PWA 1220, UNS R54620||Bar, Plate, Sheet|
|8||6Al-2Sn-4Zr-2Mo – Titanium 6-2-4-2||AMS 4981, MIL-T-9047||Bar, Wire Sheet, Plate, Forgings, Fittings, Flanges, Seamless Pipe, Seamless Tube, Welded Pipe, Welded Tube|
|9||6Al-2Sn-4Zr-6Mo – Titanium 6-2-4-6||AMS 4981||Bar, Plate, Sheet|
|10||8Al-1Mo-1V – Titanium 8-1-1||MIL-T-9046, MIL-T-9047, AMS 4972, AMS 4915, AMS 4973, AMS 4955, AMS 4916||Forgings, Bar, Sheet, Plate, Strip, Extrusions, Wire|
|11||Titanium 15V-3Cr-3Sn-3Al||AMS 4914, ASTM B265||Sheet, Foil|
|12||10V-2Fe-3Al||AMS 4983, AMS 4984, AMS 4986, AMS 4987||Bar, Forgings, Plate, Sheet, Seamless Pipe, Seamless Tube, Welded Pipe, Welded Tube, Wire|
The alloy-based titanium grades include Grade-5, 6, 9, 12, 19, 23, and others. These types of alloys have excellent toughness and high strength combined with good welding and fabrication properties. Grade 9 is used at higher temperatures than the others. Grade 12 has enhanced corrosion-resistance because of different chemical compositions. Grade 19 and 23 offer high resistance to stress and creep. Other grades, such as 6Al-6V-2Sn – Titanium 6-6-2 and Titanium 6Al-2Sn-4Zr-2Mo – Titanium 6-2-4-2, are two-phased alloys called alpha-beta alloys. They are heat-treatable alloys with lower toughness and ductility but high strength. Cold forming and welding are difficult with these types of grades because of their high strength. These grades are good for welding by the inert gas shielded and fusion welding process although the area affected will have less toughness and ductility than the original material.
The production of titanium metal is carried out by a process called the Kroll process. This process has five stages. The first stage is called extraction, the second is called purification, the third is called sponge production, the fourth involves alloy creation, and lastly, the fifth step is forming and shaping. Because every step is time-consuming and costly, no industry yet performs all five. Most industries carry out a single stage of this process. For example, some manufacturers specialize in sponge production, and others only create the alloys.
The first step of the Kroll process is the extraction of titanium ores. The manufacturer receives the titanium ores from mines. These ores can be in the form of ilmenite, rutile, or any other mineral of titanium. Rutile is usually used in its natural form. However, ilmenite needs processing that becomes the first step to remove the iron so that the remaining part will have 85% or titanium dioxide. For this process, these ores are placed inside a fluidized bed reactor with chlorine and carbon and are heated to an elevated temperature of 900 °C. The chemical reaction takes place, which results in the creation of titanium tetrachloride in impure form and carbon monoxide as a by-product. The impurities are present in the TiCl4 because after removing iron, titanium dioxide is not yet pure.
In this step, the TiCl4 is put inside a large distillation tank for heating. The impurities present are separated in this step by fractional distillation and precipitation methods. These two methods remove all impurities, including vanadium, silicon, magnesium, zirconium, and iron.
The third stage of the Kroll process is sponge formation. In this stage, the purified titanium tetrachloride is emptied into a stainless steel reactor vessel in liquid form. After the transfer, the magnesium is added to the vessel and the mixture is heated to the temperature of 1100 °C in order for magnesium to react with chlorine and produce magnesium chloride. There is a chance that oxygen and nitrogen might be present in the air, so argon gas is pumped into the vessel to remove the air to avoid any reaction with oxygen and nitrogen. The titanium left in the vessel is not pure and in solid form because the melting point of titanium is much higher. This titanium solid is now removed from the vessel by a boring process and treated with a mixture of water and hydrochloric acid. This is to remove any excess of magnesium and magnesium chloride. At the end of this stage, the titanium obtained is in sponge form, hence the name sponge formation.
In the fourth stage, the pure titanium sponge is mixed with different alloys and scrap metals to create usable alloys with the help of a consumable-electrode arc furnace. After melting and mixing all required metals in the required proportion, the mass is then compacted and welded to form a sponge electrode. This sponge electrode is melted in a vacuum arc furnace to form ingots. These ingots are usually melted again and again to fabricate commercially acceptable ingots.
In the last stage of the Kroll process, the ingots are removed from the furnace, inspected for defects, then sent out to be used to create titanium alloy goods. The properties of each ingot are checked to ensure they meet the requirements of customers. The ingots go through various processes such as welding, forming, casting, forging, powder metallurgy, etc. to be shaped into the finish well. It all depends upon the specification of the required product.
During the Kroll process, when the titanium is separated from the impurities, a significant amount of magnesium and magnesium chloride is left behind. This by-product of the Kroll process is recycled immediately in a recycling cell. The recycling cell separates the magnesium and chlorine into their stable forms. I.e., magnesium in solid form and chlorine in gas form. The chlorine gas is collected from the top of the recycling cell, and both of these components are used again in the Kroll process.
Titanium plays a significant role in the medical industry because of its biocompatibility. It is a non-toxic material that has been used in many surgical tools and implants. From hip ball socket replacement to dental implants, titanium has been used in the medical industry for various purposes. These implants can stay in place for more than 20 years. The titanium implants usually contain about 4% of vanadium and 4% to 6% of aluminum.
Titanium has an ability to Osseo-integrate, which allows us to use it in dental implants and orthopedic implants that can last for 30 years. Due to lower modulus elasticity, titanium implants allow the skeletal load to be distributed equally between the bone and implant, resulting in the reduction of bone degradation due to stress and periprosthetic bone fracture. Titanium has greater stiffness than the human bone, which can result in bone deterioration in the case of increased load.
Titanium is mostly refined into titanium dioxide, which is a white permanent pigment. This white pigment is used in papers, toothpaste, plastics, and paints. Paints with titanium dioxide perform better in severe temperatures and humid environments. It also serves its purpose in cement, optical opacities in papers, and gemstones. This is also added to graphite composite finishing rods and golf clubs to increase their strength. Titanium dioxide is a chemically inert compound that is resistant to corrosion and does not fade in sunlight. It also has a very opaque appearance, which makes it suitable for use as pigments in the manufacturing of the majority of household plastics. In addition to significant uses as a pigment, titanium dioxide is also used in sunscreens due to its high refractive index and optical dispersion.
Titanium has high corrosion resistance, high fatigue resistance, high tensile strength to density ratio, high crack resistance, and the ability to withstand high temperature. It is considered the ideal material for manufacturing aircraft, missiles, and armor plating. It is utilized in the manufacturing of critical structural parts, landing gear, exhaust ducts, firewalls, and hydraulic systems. In fact, titanium accounts for almost 50% of materials used in an aircraft. The titanium alloy used consists of aluminum, nickel zirconium, vanadium, and other elements.
Titanium is durable and biologically inert, which has increased its popularity in the jewelry industry. Its inertness makes it a popular choice among people with allergies and among people who live in a humid environment. Its durability, dent resistance, light weight, and corrosion resistance make it useful for manufacturing wristwatches and watch cases. Some artists use titanium for fabricating sculptures and other decorative objects. Titanium is also mixed with gold to produce a 24-karat gold alloy, which results in an alloy harder than pure 24-karat gold. Anodized titanium has optical interference fringes and a variety of bright colors, which make it popular for body piercings too.
Titanium is a corrosion-resistant material; this makes it ideal for use in the marine industry. Naval ships' hulks are made of titanium alloys because of their corrosion resistance to seawater. Titanium is also used to manufacture propeller shafts, heat exchanges, rigging, heat chillers for saltwater aquariums, drivers‘ knives and finishing lines, and leaders. Additionally, it is used in housing and ocean deployed surveillance equipment and monitoring devices.
Titanium is used in the automotive industry, particularly where low weight and high strength rigidity are required. It is also cost-effective considering metal is generally too expensive to be used in huge amounts. It is used to manufacture exhaust and intake valves inside engines because of its heat resistance and high strength.
Titanium has a great affinity for oxygen and other elements, so it is impossible to find titanium in a metallic state in nature. The titanium concentration in the air of urban areas is below 0.1 µg/m3 However, in some areas, especially where factories are close, 1.0 µg/m3 has been reported too. This concentration affects drinking water supplies and food items. Because of this, the intake of titanium by humans has been reported from 300 µg/day to 2 mg/day.
Clinical studies on animals and humans have shown that if titanium dioxide is inhaled, it remains biologically inert. The possibility of weak fibrosis due to exposure to titanium dust is more likely to be caused by concomitant exposure to other components present in titanium dust rather than titanium dioxide. However, in animals, titanium nitrides, titanium hydrides, and titanium carbides can cause fibrogenic effects. These compounds of titanium can also cause kidney and liver dystrophy in animals as well. However, titanium tetrachloride has a different effect on both humans and animals. In humans, this compound can cause skin burns and strong irritation in the eyes. Additionally, titanium in powdered form is known to induce lymphosarcoma and fibrosarcoma, but only in rats when they are injected. There is no evidence that it has any carcinogenic effect in humans. In addition to this, titanium has been frequently used in lung clearance studies. The studies have not shown any detrimental effects of titanium dioxide in the lungs.
Titanium has a dominant role in the implant and prosthetic industry. The studies on animals and humans have shown that the presence of titanium in implants and prosthesis have no effect on human tissues. The osseous and soft tissue present in animal and human bodies has extreme tolerance of titanium. This means there are no reports of irritation or delay in healing of wounds, and there is an encapsulation of the metal by fibrous tissues. Titanium compounds such as dioxides, oxides, tannates, and salicylates play an important role in dermatological and cosmetic formulations. They do not show any adverse effects on human skin. However, exposure to various titanium compounds has been linked to slight pulmonary fibrosis.
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