Metallic Alloys 

Metallic Alloys 

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Metal has been used extensively in the manufacturing of orthopedic implants in a multitude of different forms. Multiple different materials throughout history have been tested as replacements for bone. Materials as diverse as ivory, wood, rubber, acrylic, and Bakelite have been used in the manufacture of prosthetic implants.

The extensive use in modern times of metallic alloys is related to the availability and success at the beginning of the 20th century of several different alloys made of the noble metals. Implants made from iron, cobalt, chromium, titanium, and tantalum are commonly used (see the images below). Clinical studies have demonstrated that alloys made from these metals can be used safely and effectively in the manufacturing of orthopedic implants that are left in vivo for extended periods. The mechanical, biologic, and physical properties of these materials play significant roles in the longevity of these implants.

Implants are made in three basic ways:

Alloys that provide for a long-term stable implant need to have a high level of corrosion resistance as well as certain mechanical properties (see Immune Response to Implants).

Dalury et al followed 96 patients for 5 years who had undergone total hip arthroplasty with single titanium stems. [1] The average Harris Hip score was 96 points (range, 73-100 points) at final follow-up, and radiographically, all stems were ingrown. No stem had more than 3 mm of subsidence, and there were no leg-length discrepancies greater than 5 mm. The authors concluded that the titanium stem is a versatile option for total hip arthroplasty.

Grupp et al reported their experience regarding failed modular titanium neck adapters, in combination with a titanium alloy modular short hip stem, after hip arthroplasty, as a result of fretting or corrosion. [2] They were then replaced by cobalt-chromium adapters. The authors noted that by the end of 2008, 1.4% (68 of approximately 5000) of the implanted titanium alloy neck adapters failed at an average of 2 years’ time (0.7 to 4.0 years) postoperatively.

Grupp et al concluded that failure of modular titanium alloy neck adapters can be initiated by surface micromotions due to surface contamination or highly loaded implant components. [2] In the study, according to the authors, the patients at risk were men with an average weight over 100 kg. They added that with a cobalt-chromium neck, micromotions can be reduced by a factor of 3 and the incidence of fretting corrosion substantially lowered.

An element is considered metallic if a positive charge is demonstrated on an electrolysis test. [3] This test consists of dissolving the element in acid and running a current through the solution. When such elements are fully reduced, their metallic nature is recognized and they and their alloys are called metals; when oxidized, they can serve as ceramic materials. [4]

Metals have several properties that are specific to them, including malleability, which allows the shaping of metal into implants, and ductility, which refers to the ability to draw out metal in the shape of wire and is an important property in allowing the manufacture of intramedullary rods, screws, and long stems. By combining several metallic elements together in alloys, improved properties can be achieved beyond those of a single element. The alloys used in orthopedic surgery need to have certain specific properties. Because the alloy of the implant is bathed in body fluid, a low rate of corrosion and relative inertness are imperative in the material.

All metallic alloys have a modulus of elasticity significantly higher than that of bone. This mechanical incompatibility causes implants to be structurally stiffer than bones. Alloys with elastic moduli closer to bone may cause less stress shielding.

Different metals can form a battery effect when in solution in the body. The galvanic series provides electrochemical comparisons that allow prediction of corrosion between two different metals when they are in physical contact in saline solution. [5] Galvanic corrosion occurs if stainless steel surgical wire is wrapped over a cobalt- or titanium-based alloy femoral component or if a cobalt-chromium femoral head is placed on a titanium alloy femoral stem, so this metal mismatch is not recommended. Cobalt- and titanium-based alloy components may be used in contact with each other, and stainless steel components, such as sutures, may be used with either if actual physical contact is avoided.

The introduction of steel plates for fracture treatment is credited to Sherman. [6] Surgical stainless steel alloys (316L) made with varying amounts of iron, chromium, and nickel are presently used in the manufacture of prostheses. The low carbon (L) in surgical stainless steel diminishes corrosion and decreases adverse tissue responses and metal allergies. Although many implants are still manufactured from this excellent material, its use is currently relegated mainly to plates, screws, and intramedullary devices that are not meant to be weightbearing for an extended period. Fatigue failure and relatively high corrosion rates make it a poor candidate for the manufacture of modern joint replacement implants. [7]

Chromium-containing iron (and cobalt base) alloys have a chromium oxide–based surface that is a result of passivation or oxidation of the surface. The chromium oxide forms a very thin invisible shield that provides resistance to biodegradation. Because this oxide layer slowly dissolves in vivo, these alloys have a relatively high rate of corrosion. This is evident as a propensity toward both fretting and crevice corrosion, which limits the possibility for biologic fixation or for the manufacture of modular implants.

Venable and Stuck discovered the battery effects of metals in the body through their testing of the electrolytic effects of various metals on surrounding tissue and bone. [3] These tests demonstrated the low level of corrosion of the cobalt-based alloy vitallium.

Alloys made of cobalt, chromium, and molybdenum can be used in various different porous forms to allow for biologic fixation by ingrowth. These alloys are among the least ductile when compared to either iron- or titanium-based alloys, making manufacture of these intramedullary rods and spinal instrumentation more difficult. These alloys have some of the highest moduli of elasticity observed in orthopedic implants, and as a result, this was a factor in the stress shielding and thigh pain observed in the first generation of biologically fixed femoral hip implants made with cobalt alloys. [8]

These alloys are well suited for the production of implants that are designed to replace bone and to be loadbearing for an extended period, if not permanently.

The Austin Moore prosthesis and the Thompson prosthesis were manufactured from the cobalt-based alloys. The first-generation biologically fixed implants (ie, porous-coated anatomic [PCA] and anatomic medullary locking [AML] implants) were manufactured of this material. Numerous modern prostheses are still manufactured from this excellent alloy and are used in both cemented and porous forms for hip and knee replacement.

In 1951, Levanthal introduced titanium as a metal for surgery. [9] Titanium-based alloys have excellent properties for use in porous forms for biologic fixation of prostheses. The most common is Ti-6 aluminum Ti-4 vanadium (Ti6Al4V), but other more modern alloys are coming into use. Because titanium-based alloys have a lower moduli of elasticity than cobalt-based alloys or surgical stainless steel, they have not been found to be as reliable when used as a cemented hip replacement. Moreover, their use in total knee replacements has been limited to the nonarticulating parts of the tibial component because of significant wear observed in femoral heads. [10]

Titanium’s high level of biocompatibility, low level of corrosion, and modulus of elasticity closer to that of bone allow for its use in numerous porous implants that have yielded excellent long-term results. The low level of corrosion allows for the construction of modular implants that saves in inventory and allows for more precise implant fit. [11]

Current use of titanium in various forms is in the production of fracture plates and intramedullary rods and in the production of both femoral and acetabular implants designed for bone ingrowth. Fracture fixation components fabricated from titanium-based alloys are also used preferentially when the implant site is known to be infected or when postoperative shadow-free imaging is desired.

Industry has been modifying the surface area of titanium implants with many proprietary coatings. [12] Attempts at mimicking the microscopic structure of cancellous bone has been extremely effective in increasing the scratch fit noted with these implants. [13] Time will tell whether or not the longevity of these coatings will result in improved long-term ingrowth of components.

Tantalum is also remarkably resistant to corrosion and has been used as an ingredient in super alloys, principally in aircraft engines and spacecraft, though 50% of current use is in the form of powder metal for the manufacture of transistors and capacitors. Tantalum can be fabricated in a highly porous form, which has a modulus of elasticity closer to that of bone than stainless steel or the cobalt-based alloys. Tantalum balls have been used in studies that have required bone markers; however, it has not been used in the manufacture of implants until recently. Because of its remarkable resistance to corrosion, tantalum is well suited to a biologic ingrowth setting.

Current use of tantalum has been in the form of a honeycombed structure that is extremely porous and conducive to bone ingrowth. It is available in several forms for bridging bone defects, but its use in the manufacture of femoral stems remains to be seen. Tantalum appears to be a promising metal for use in acetabular reconstruction, but long-term studies are required. [14, 15, 11, 16, 17]

The combination of metallic alloys with other biomaterials can result in implants with improved mechanical and physical properties. Current attempts in designing composite implants have not yielded highly successful results; however, the possibilities for future improvements are promising.

Different alloys demonstrate different rates of wear. The hardness of an alloy and the smoothness of the bearing surfaces determine its relative rate of wear. Cobalt-chromium-molybdenum alloys and alloys made of stainless steel are more wear-resistant than titanium or titanium-based alloys. When breakdown with titanium-based alloys occurs, it is often observed as black areas within the tissues.

Metallic ion release occurs in vivo, and numerous studies demonstrate soluble and precipitated corrosion products, as well as metallic wear debris, in the liver, spleen, lungs, and even remote bone marrow of the iliac crest. The constant motion of the metal-on-metal prosthesis causes a wearing away of the passivated surface and an increase in metallic ion release. The recent interest in metal-on-metal prostheses raises questions of biocompatibility and possible carcinogenic effects that these metallic ions can cause. [18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30]

Several metal-on-metal prostheses have been recalled, and concerns have been expressed about the long-term safety of metal-on-metal prostheses. In April 2010, the United Kingdom’s Medicines and Healthcare Products Regulatory Agency issued a medical device alert on metal-on-metal hip replacements. Recommendations have included specific blood tests and imaging for patients with painful metal-on-metal hip replacements. Metal ion testing and evaluation for effects of metal debris such as possible local nerve palsy, local swelling, and joint dislocation or subluxation should be considered by orthopedic surgeons treating patients with metal-on-metal prostheses.

The consensus of the sixth advanced hip resurfacing course (Ghent, Belgium, May 2014), formulated by an international faculty of expert metal-on-metal hip resurfacing surgeons, was that hip resurfacing should be limited to high-volume hip surgeons who are experienced in hip resurfacing or have been trained to perform hip resurfacing in a specialist center. [31]

It is to be hoped that further developments in metallurgy will allow the development of new alloys that, when compared to current alloys, will have better mechanical and physical properties yielding better long-term results with implants.

Concurrent developments in other biomaterials, including ceramics and modified polyethylenes (eg, cross-linked polyethylene) may yield improvements in the longevity of total joint replacements either with the success of alternative bearing surfaces or with the use of composite materials. The total joint replacement that will last the life of the patient may be a reality one day. [32, 33]

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Grupp TM, Weik T, Bloemer W, Knaebel HP. Modular titanium alloy neck adapter failures in hip replacement – failure mode analysis and influence of implant material. BMC Musculoskelet Disord. 2010 Jan 4. 11(1):3. [Medline]. [Full Text].

Venable CS, Stuck WG, Beach A. The effects on bone of the presence of the metals; based upon electrolysis. An experimental study. Ann Surg. 1937. 105:917.

Rahaman MN, Bal BS, Garino J, Ries M, Yao J. Ceramics for Prosthetic Hip and Knee Joint Replacement. J Am Ceram Soc. 2007. 90:1965-1988.

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Sherman WO. Vanadium steel plates and screws. Surg Gynecol Obstet. 1912. 14:629.

Yoo YR, Jang SG, Oh KT, Kim JG, Kim YS. Influences of passivating elements on the corrosion and biocompatibility of super stainless steels. J Biomed Mater Res B Appl Biomater. 2008 Aug. 86B(2):310-20. [Medline].

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Levanthal GC. Titanium: a metal for surgery. J Bone Joint Surg. 1951. 33:473.

Marx R, Faramarzi R, Jungwirth F, Kleffner BV, Mumme T, Weber M, et al. [Silicate coating of cemented titanium-based shafts in hip prosthetics reduces high aseptic loosening]. Z Orthop Unfall. 2009 Mar-Apr. 147(2):175-82. [Medline].

Jafari SM, Bender B, Coyle C, Parvizi J, Sharkey PF, Hozack WJ. Do tantalum and titanium cups show similar results in revision hip arthroplasty?. Clin Orthop Relat Res. 2010 Feb. 468(2):459-65. [Medline]. [Full Text].

Hatamleh MM, Wu X, Alnazzawi A, Watson J, Watts D. Surface characteristics and biocompatibility of cranioplasty titanium implants following different surface treatments. Dent Mater. 2018 Apr. 34 (4):676-683. [Medline].

Ozdemir Z, Ozdemir A, Basim GB. Application of chemical mechanical polishing process on titanium based implants. Mater Sci Eng C Mater Biol Appl. 2016 Nov 1. 68:383-396. [Medline].

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Levine B, Sporer S, Della Valle CJ, Jacobs JJ, Paprosky W. Porous tantalum in reconstructive surgery of the knee: a review. J Knee Surg. 2007 Jul. 20(3):185-94. [Medline].

Lachiewicz PF, Soileau ES. Tantalum components in difficult acetabular revisions. Clin Orthop Relat Res. 2010 Feb. 468(2):454-8. [Medline]. [Full Text].

Harrison AK, Gioe TJ, Simonelli C, Tatman PJ, Schoeller MC. Do porous tantalum implants help preserve bone?: evaluation of tibial bone density surrounding tantalum tibial implants in TKA. Clin Orthop Relat Res. 2010 Oct. 468 (10):2739-45. [Medline].

Benz EB, Sherburne B, Hayek JE, et al. Lymphadenopathy associated with total joint prostheses. A report of two cases and a review of the literature. J Bone Joint Surg Am. 1996 Apr. 78(4):588-93. [Medline].

Case CP, Langkamer VG, James C, et al. Widespread dissemination of metal debris from implants. J Bone Joint Surg Br. 1994 Sep. 76(5):701-12. [Medline].

Nyren O, McLaughlin JK, Gridley G, et al. Cancer risk after hip replacement with metal implants: a population-based cohort study in Sweden. J Natl Cancer Inst. 1995 Jan 4. 87(1):28-33. [Medline].

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Vendittoli PA, Roy A, Mottard S, Girard J, Lusignan D, Lavigne M. Metal ion release from bearing wear and corrosion with 28 mm and large-diameter metal-on-metal bearing articulations: a follow-up study. J Bone Joint Surg Br. 2010 Jan. 92(1):12-9. [Medline].

Durrani SK, Noble PC, Sampson B, Panetta T, Liddle AD, Sabah SA, et al. Changes in blood ion levels after removal of metal-on-metal hip replacements: 16 patients followed for 0-12 months. Acta Orthop. 2014 Jun. 85 (3):259-65. [Medline]. [Full Text].

Lainiala O, Reito A, Elo P, Pajamäki J, Puolakka T, Eskelinen A. Revision of Metal-on-metal Hip Prostheses Results in Marked Reduction of Blood Cobalt and Chromium Ion Concentrations. Clin Orthop Relat Res. 2015 Jul. 473 (7):2305-13. [Medline].

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Van Der Straeten C, De Smet KA. Current expert views on metal-on-metal hip resurfacing arthroplasty. Consensus of the 6th advanced Hip resurfacing course, Ghent, Belgium, May 2014. Hip Int. 2016 Jan-Feb. 26 (1):1-7. [Medline].

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Arturo Corces, MD Miami Institute for Joint Reconstruction

Arturo Corces, MD is a member of the following medical societies: American Academy of Orthopaedic Surgeons

Disclosure: Nothing to disclose.

Michael Garcia University of Florida at Gainesville

Disclosure: Nothing to disclose.

Francisco Talavera, PharmD, PhD Adjunct Assistant Professor, University of Nebraska Medical Center College of Pharmacy; Editor-in-Chief, Medscape Drug Reference

Disclosure: Received salary from Medscape for employment. for: Medscape.

Murali Poduval, MBBS, MS, DNB Orthopaedic Surgeon, Senior Consultant, and Subject Matter Expert, Tata Consultancy Services, Mumbai, India

Murali Poduval, MBBS, MS, DNB is a member of the following medical societies: Association of Medical Consultants of Mumbai, Bombay Orthopedic Society, Indian Orthopedic Association, Indian Society of Hip and Knee Surgeons

Disclosure: Nothing to disclose.

Metallic Alloys 

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