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Surface Modification of Titanium – Part 1 – General Introduction & Pre-treatment

Geschätzte Lesezeit: 13 - 25 Minuten
A representative pre-treatment plant A representative pre-treatment plant Photo: Dr. Sharma

The outstanding properties of titanium and titanium alloys make them an ideal manufacturing material for the production of components for aerospace, automotive and surgical implants, among others. However, bare titanium cannot meet all functional requirements. To further improve chemical, mechanical and biological properties, the surface of titanium is modified. This article reviews recent advances in titanium alloy electrolytic surface modification methods in 6 parts.

Fig. 1: Elemental (left) and material properties (right) of TitaniumFig. 1: Elemental (left) and material properties (right) of TitaniumOwing to their high tensile strength to density ratio, high fatigue resistance, anti-magnetic properties, and ability to withstand moderately high temperatures without creeping, titanium alloys are ideally suited for manufacturing of structural components of aerospace systems. In addition, titanium alloys have superior resistance to many corrosive environments and excellent composite compatibility. Titanium has found a niche in many other industrial applications where light weight and good tribological and corrosion resistance properties are required, e.g., automobile, submarine vessels, and chemical plants. Due to their low elastic modulus, good fatigue strength, formability, corrosion resistance, excellent biocompatibility and good osseointegration properties, titanium alloys are promising candidates in the fabrication of surgical implants. The properties of Titanium are highlighted in Figure 1.


Structural materials for aerospace and related applications must withstand the static weight of the craft and the additional loads related to lift-off, take-off, taxing, landing, manoeuvres, turbulence etc. They should have relatively low densities for mass reduction/fuel efficiency and adequate mechanical strength. In addition, they must have the damage tolerance to withstand extreme environmental conditions. The typical share of different materials in aeronautics is illustrated in Figure 2.

Graphics: crosstraxx Graphics: crosstraxx

Titanium has a relatively low density, thermal conductivity, thermal expansion coefficient, and elastic modulus; moderate strength; good corrosion resistance in various environments [1]. Titanium is an allotropic material. Its metallurgy is dominated by the crystallographic transformation which takes place in the pure metal at 882 °C. Below this temperature, pure titanium has a hexagonal close packed (hcp) structure called alpha (α) titanium. But above this temperature it transforms to a stable body-centred cubic (bcc) structure, which is referred to as beta (β) titanium [2–5]. The fundamental effect of alloying additions to titanium is alteration of the transformation temperature with specific phase structure. Titanium alloys can therefore be grouped into three main categories α-type (hcp), β-type (bcc) and (α+β)-type. Their properties are dependent on microstructure which, in turn, depends on the chemical composition and thermomechanical processing. Table 1 summarizes the typical composition and mechanical properties of commercially pure titanium and representative titanium alloys.

Tab. 1: Composition and properties of some titanium alloys [2] 

Alloy / ASTM Grade (Density, g/cm3)


Chemical Composition mass %, balance Ti


Yield Strength, (MPa)

Elongation at Failure (%)

Elastic Modulus (GPa)

Thermal conductivity (W/mK)

CPTi / Grade 1 (4.5)


N:0.03, C:0.08, H:0.015, Fe:0.20, O:0.18.






CPTi / Grade 2 (4.5)


N:0.03, C:0.08, H:0.015, Fe:0.30, O:0.25






CPTi / Grade 3 (4.5)


N:0.03, C:0.08, H:0.015, Fe:0.30, O:0.35






CPTi / Grade 4 (4.5)


N:0.03, C:0.08, H:0.015, Fe:0.50, O:0.40






Ti5Al2.5Sn TA7 / Grade 6 (4.48)


N:0.05, C:0.08, H:0.02, Fe:0.5, O:0.2; Al: 4-6, Sn: 2-3






Ti6Al4V / Grade 5 (4.43)


N:0.05, C:0.10, H:0.025, Fe:0.30, O:0.20; Al: 5.5-6.75, V: 3.5-4.5






Ti6Al4V ELI / Grade 23 (4.43)


N:0.05, C:0.08, H:0.025, Fe:0.25, O:0.13; Al: 5.5-6.75, V: 3.5-4.5






Ti6Al7Nb (4.52)


N:0.05, C:0.08, H:0.009, Fe:0.25, O: <0.2; Al: 5.5-6.5, Nb: 6.5-7.5






Ti13V11Cr3Al (4.84)


N:0.05, C:0.05, H:0.025, Fe:0.35, O: <0.17; V: 12.5-14.5, Cr: 10-12, Al: 2.5-3.5






Ti29Nb13Ta4.6Zr, TNTZ (4.48)


Nb: 29, Ta: 13, Zr: 4.6 (nominal)





The alloying elements added to titanium are classified as α-, β-, or neutral stabilizers [6]. The position of the alloying element in the lattice crystal may be interstitial (e.g., O, N, C, H, Fe, Cr, Mn, Ni) or substitutional (e.g., Al, Mo, V, Sn, Zr). Elements having extensive solubility (such as Al, O, N or C) in the α-phase characteristically raise the transformation temperature and are called α-stabilisers. Elements that depress the transformation temperature, readily dissolve in and strengthen the β-phase and exhibit low α-phase solubility are known as β-stabilisers. They can be divided into two categories according to their constitutional behaviour with titanium, viz., β-isomorphous elements, and β-eutectoid elements.

Fig. 2: Typical share of different materials in aerospace applicationsFig. 2: Typical share of different materials in aerospace applications

β-isomorphous elements promote the stability of phase by complete mutual solubility with β-titanium. Increasing addition of the solute element progressively depresses the transformation temperature. Mo and V are the most important β-isomorphous elements, while Nb and Ta have also found application in some alloys. β-eutectoid elements have restricted solubility in β-titanium and cause eutectoid transformations of β-phase by forming intermetallic compounds. Eutectoid elements include Fe, Cr, Cu, Ni, Co, Mn, and Si. H is also classified in the category of eutectoid alloying elements. Tin and zirconium metals have appreciable solubility in both α and β phases and as their addition does not markedly influence the transformation temperature they are normally classified as neutral additions.

α-alloys are non-heat treatable and are often easily weldable. They have low to medium strength, good notch toughness, reasonably good ductility and possess excellent properties at cryogenic temperatures. In general, α- or near α-Ti alloys offer higher temperature creep strength and oxidation resistance than β-Ti alloys [6]. (α+β)-alloys are heat treatable to varying extents and most are weldable with the risk of some loss of ductility in the weld area.

They have medium to high strength levels. Their hot forming qualities are good but cold forming is often difficult. Creep strength is not usually as good as in most α-alloys. β- or near β-alloys are readily heat treatable, usually weldable, and hold high strength up to intermediate temperature levels. In the solution treated condition, cold formability is generally excellent.

The commercially pure (CP) titanium, CP-Ti, is available in four grades numbered 1 to 4, according to the purity and the processing oxygen content [7–9]. These grades differ in corrosion resistance, ductility and strength, and it is grade 4 CP-Ti, with the highest oxygen content (around 0.4 %) and best overall mechanical strength, that is most widely used for dental implants [3, 9]. In general, α-titanium alloys have superior creep behaviour and corrosion resistance than β-titanium alloys [6] and are therefore frequently used to make compressor disks and blades of aeronautic engines. β-titanium alloys on the other hand exhibit higher strength and fatigue behaviour than the α-titanium alloys, thus they are selected for manufacturing of high-stressed aircraft components, e.g., landing gear, springs and airframe parts [10, 11]. A drawback of these alloys is their relatively low ductility, which can be mitigated through tailoring the composition and suitable heat treatments [12, 13].

Since its first introduction in the early 1950s [14–16], (α-β)-Ti alloy Ti6Al4V (or ASTM Grade 5), is the workhorse alloy of the titanium industry. It is most extensively used titanium alloy in automotive, aerospace, chemical, marine and biomechanical implants [3, 15–19]. This alloy is fully heat treatable and is used up to 400 °C. Owing to its superior strength, lower Young’s modulus and excellent corrosion resistance [20], today it covers about 50 % of total titanium world production [14, 15]. Titanium and its alloys are widely used in orthopaedics and dentistry due to their good biocompatibility. Extra Low Interstitials alloy –Ti6Al4V ELI (Grade 23), where in particular the maximum oxygen content is lowered to 0.13 %, provides improved ductility and better fracture toughness. Ti6Al4V ELI also has high resistance to stress corrosion cracking (SCC) in sea water that makes it an obvious choice for fabrication of offshore equipment. About 40 % of today‘s biomedical implant materials are based in titanium [21]. Due to cytotoxic vanadium in Ti6Al4V alloy, another alternative high strength and biocompatible (α+β)-alloy, Ti6Al7Nb is employed for hip prostheses and other implants [22, 23]. Development of titanium and titanium-based alloys as biomaterials for orthopaedic applications are reviewed elsewhere [24, 25].

The main drawback with titanium is its inherent poor tribological properties, high and unstable coefficient of friction (COF) [26], low abrasive and adhesive wear resistance [26, 27], low hardness [28, 29], strong tendency to galling and seizing [30], low load-carrying capacity [30, 31], and its reactivity towards atmospheric oxygen. This significantly limits its use in wear-related engineering applications. Further, the titanium is not suitable for long-term clinical usage due to its bio-inertness, it can’t be bonded to living bone directly after implantation. To overcome these limitations and to improve the chemical, mechanical, and biological properties, a suitable surface modification of titanium is of the utmost importance [32, 33].

Surface modification technologies provide an effective protection against both wear and corrosion, and improve the tribological performance and osseointegration of titanium [34–37]. This article aims to provide a summary of the state-of-the-art advances in electrochemical surface modification techniques of titanium and its alloys to enhance their performance in service conditions.


Fig. 3: Metal components on their way to a blasting machine. Sandblasting is part of the pre-treatment of titanium and its alloysFig. 3: Metal components on their way to a blasting machine. Sandblasting is part of the pre-treatment of titanium and its alloysPre-treatment methods for titanium alloys are important for both deposition of the subsequent coating processes as well as surface modifications of the implants. The function of these pre-treatments is to remove the unstable surface layer, contaminants and adsorbed species, and to unify the surface in terms of internal stress, morphology and specific surface area. The pre-treatment techniques modify the surface morphology of material‘s surface at micro-nano scale to enhance its suitability for subsequent operations including osseointegration [38–40].

There are variety of pre-treatment procedures or combination of these that govern the morphology and the adhesion of subsequent coatings. The most common pre-treatments are sandblasting, grinding, fine abrasive polishing, chemical or electrochemical etching, electrochemical polishing, anodizing, micro arc oxidation, etc. [41–46]. An image of a typical sandblasting plant is shown in Figure 3.

The grit method consists in blasting the job with hard ceramic particles, such as Al2O3, or TiO2. The blasting material may be embedded into the implant surface and residue may remain even after ultrasonic cleaning, acid etching and sterilization. In some cases, these particles have been released into the surrounding tissues and have interfered with the osseointegration of the implants. Hence, the care must be taken in the selection of blasting material and the process of blasting. Acid etching involves immersing a metal substrate in an aqueous acid solution to remove a loose layer of oxide from its surface. The choice of particular acid depends upon the alloy composition, thermomechanical treatment employed and type of scale formed on the surface of the job. The holes caused by shot blasting consist of sizeable pores (10–30 µm) depending on pressure, grain size, blasting distance, blasting angle and time [47]. Addition of an acid etching could further produce sub-micron holes (< 1 µm, small holes in the large holes) with specific surface roughness and uniform nanopores. This helps to increase the contact area of the bone for an implant and to reduce the healing time of the implant surgery.

Biomaterial surfaces usually need to be hydrophilic in order to favour cell attachment, and the wettability of a solid surface can be quantified by measuring the contact angle. The wettability of the bare titanium substrates and different pre-treated surfaces varied from hydrophobicity to hydrophilicity. This change in contact angle, the angle between the solid surface and the liquid drop surface, is controlled by the complex surface chemistry, and is influenced by many other factors, such as the method of surface preparation, surface roughness, surface compositions, and chemical states. Smooth titanium surface shows a hydrophobic behaviour with a contact angle of about 90°. The wettability and the roughness of commercially grade 2 pure titanium was found to increase after pre-treatment in the following order: mechanical polishing, acid etching, sandblasting and sandblasting-acid etching [48]. For grade 4 titanium surfaces the same increasing trend of wettability and roughness was observed after machining, acid etching, sandblasting-acid etching and anodization [49]. After anodizing, its wettability increases. It becomes more hydrophilic; the contact angle reduces to less than 20°. Many studies have shown that a more wettable surface (hydrophilic) with a larger specific area (roughness) enhances the adsorption of proteins. This promotes osteogenic cell migration, and osseointegration speeds up [50-54].

The electrochemical and ion sputter etching techniques are used as very efficient surface finishing techniques, in particular for chemically-resistant and weakly-etchable β-titanium alloys [38, 55-57]. The high dissolution rate of material has to be controlled by optimization of conditions like electrolyte composition, temperature, current density and potential [58-60]. Similarly, the impact of various variables of ion sputter etching of titanium has been studied by many researchers [61-63]. The wettability and type of morphology, (size and shape) varied with argon hydrogen ratio, ion current density, energy and the fluence, and temperature. Comprehensive reviews of surface pre-treatments for titanium alloys have been presented [44, 64-67].


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  • Ausgabe: 5
  • Jahr: 2023
  • Autoren: Dr. Anand Kumar Sharma

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