2003 - Surface Pretreatments For Medical Application of Adhesion

BioMedical Engineering OnLine BioMed Central
Review Open Access

Surface pretreatments for medical application of adhesion
Hans J Erli†2, Rudolf Marx*†1, Othmar Paar2, Fritz U Niethard3,
Michael Weber†1 and Dieter C Wirtz†3
Address: 1Department of Prosthetic Dentistry, Section of Dental Materials, University Hospital of the University of Technology, Aachen, Germany,
2Department for Trauma Surgery, University Hospital of the University of Technology, Aachen, Germany and 3Department of Orthopedic Surgery,
University Hospital of the University of Technology, Aachen, Germany

Email: Hans J Erli - herli@ukaachen.de; Rudolf Marx* - marx@rwth-aachen.de; Othmar Paar - opaar@ukaachen.de;
Fritz U Niethard - funiethard@orthopaedie-aachen.de; Michael Weber - mail@michaelweber.de; Dieter C Wirtz - dcwirtz@ukaachen.de
* Corresponding author †Equal contributors
Published: 18 September 2003 Received: 18 March 2003

Accepted: 18 September 2003
BioMedical Engineering OnLine 2003, 2:15
This article is available from: http://www.biomedical-engineering-online.com/content/2/1/15
© 2003 Erli et al; licensee BioMed Central Ltd. This is an Open Access article: verbatim copying and redistribution of this article are permitted in all media
for any purpose, provided this notice is preserved along with the article's original URL.
Abstract
Medical implants and prostheses (artificial hips, tendono- and ligament plasties) usually are multi-
component systems that may be machined from one of three material classes: metals, plastics and
ceramics. Typically, the body-sided bonding element is bone.
The purpose of this contribution is to describe developments carried out to optimize the
techniques , connecting prosthesis to bone, to be joined by an adhesive bone cement at their
interface. Although bonding of organic polymers to inorganic or organic surfaces and to bone has
a long history, there remains a serious obstacle in realizing long-term high-bonding strengths in the
in vivo body environment of ever present high humidity.
Therefore, different pretreatments, individually adapted to the actual combination of materials, are
needed to assure long term adhesive strength and stability against hydrolysis. This pretreatment for
metal alloys may be silica layering; for PE-plastics, a specific plasma activation; and for bone,
amphiphilic layering systems such that the hydrophilic properties of bone become better adapted
to the hydrophobic properties of the bone cement. Amphiphilic layering systems are related to
those developed in dentistry for dentine bonding.
Specific pretreatment can significantly increase bond strengths, particularly after long term
immersion in water under conditions similar to those in the human body. The bond strength
between bone and plastic for example can be increased by a factor approaching 50 (pealing work
increasing from 30 N/m to 1500 N/m).
This review article summarizes the multi-disciplined subject of adhesion and adhesives, considering
the technology involved in the formation and mechanical performance of adhesives joints inside the
human body.
Introduction physical requirements for successful implantation and

Implants and prostheses can help provide numerous use- function. Therefore, implants and prostheses usually con-
ful functions for the human body. However, a device fab- sist of composites and mixtures or alloys.
ricated from a single material usually cannot meet all
Page 1 of 18
(page number not for citation purposes)
BioMedical Engineering OnLine 2003, 2 http://www.biomedical-engineering-online.com/content/2/1/15
Over the last decade, the growth in the use of adhesives for Review
medical applications has been rapid, with many impor- Orthopedic total endoprostheses
tant developments in the technology of adhesive tech- Hip replacement surgery in the developed countries is
niques being reported. This growth has also drawn becoming more common as the population has increas-
attention to basic studies in the science of adhesion and ing life expectancy. There are two types of artificial hip
adhesives, particularly concerning stability under wet con- replacements, the cemented prosthesis focused in the
ditions. There are many analogies between adhesive present investigation, and the uncemented prosthesis,
bonds for industrial applications and the requirements for which is not being considered here.
pre-treatments and adhesives inside the human body. For
many industrial applications, stable bond strengths are Each prosthesis is made up of two parts, the femoral stem
mandatory, particularly in the presence of elevated tem- component which replaces the femoral head and neck,
perature and humidity. These conditions are also present and the acetabular cup component which replaces the
in the human body. In common for the human body and acetabulum. Both are held in place by polymethylmeth-
many industrial applications is the relative humidity of acrylate (PMMA) using cementing fixation technique. The
100%, a challenge for any adhesive joining. The elevated femoral stem is made of metal (CoCr- or Ti-alloy) and has
temperature (37°C inside the body compared with room a modular ceramic ball on its neck that fits into the acetab-
temperature) means higher diffusion rates of water mole- ular cup component and acts as a low friction bearing. The
cules through permeable materials like plastics [1]. acetabular cup is most frequently made out of ultra-high
molecular weight polyethylene (UHMWPE).
Long-term stability is crucial for attaining a useful service-
life. A bonded component may deteriorate upon exposure There are many reasons why an artificial hip replacement
of the adhesive interface to its normal operating environ- finally fails [2]. Aseptic loosening of cemented implants
ment. In the case of structural adhesive interfaces consist- causes more than 80% of clinical revisions [3–5].
ing of metallic substrates, empirical investigations Although this loosening may be due to a wide range of dif-
established many years ago revealed that water, either in ferent factors, several researchers having performed clini-
liquid or vapor form, is the most hostile environment that cal and histological studies have been able to show that
is commonly encountered. The presence of moisture, the beginning of the aseptic loosening process in femoral
rather than other components of body fluids, is responsi- stems is found in the cement-metal interface (debonding)
ble for the environmental attack, while an applied [6,7]. Supported by diffusion and capillary forces, water
mechanical load further increases the rate of adhesion molecules find their way into the bone cement and finally
loss. The loss in strength is attributed to the de-bonding of into the bone cement-metal interface, separating cement
resin from the metal by the intrusion of water, since obvi- from metal by hydrolytic degradation of the primary
ously the interface between such dissimilar materials as an bond.
organic polymer and a metal does not allow the forma-
tion of a water-resistant bond. Similar reasoning holds As a consequence of the de-bonding, micro-movement
that a similar effect occurs when the substrate is a ceramic between the implant and bone cement starts and then
or a plastic. Here, also, the presence of water is the most increases, and eventually leads to the development of
hostile environment when its molecules come into com- wear debris of cement particles, cement fissures, and
petition with the bonds between the adhesive and the cement fractures, with the formation of osteolytic reac-
prosthesis. Thus, suitable technologies need to be devel- tions within the periprosthetic bone. Loosening of the
oped to join different compound materials adhesively to prosthesis is the final result [8].
each other or to human body structures when long service
life with sufficient adhesion strengths is the goal. For Although the rate of loosening has been reduced over the
implants and prostheses, long-term stability means a low past two decades by improved cementing technology and
failure rate over the total implant time. more suitable implant materials, permanent resistance to
hydrolytic degradation of the bond of the acrylic PMMA
In the following review, some issues from the medical onto the metal surface remains an important unsolved
fields for which adhesive techniques are already estab- problem in total hip arthroplasty of the femoral stem. In
lished or for which the functionality may be improved by contrast, the weak link of the chain of bonding on the
adhesive techniques are discussed, particularly within the acetabular side is the long-term bond stability between
background of our research results. the acrylic PMMA and the acetabular bone stock. There is
no true microinterlocking between the cement and the
subchondral sclerotic acetabular bone after reaming the
acetabulum. Several studies of primary total hip arthro-
plasties with cemented cups showed an increasing failure
Page 2 of 18
rate after 8 to 10 years of implantation. On the acetabular ger of water at the interface is primarily not determined by
side, the bond between the polymer polyethylene and the the rate of permeation of water through the polymer
polymer bone cement is not of primary concern in reduc- matrix, but by the amount of moisture finally retained at
ing the rate of loosening, nevertheless it should not be the interface.
forgotten.
Metal surfaces form metal-oxides, oxide-hydrates, and
In this review, the metal stem and the plastic acetabular hydroxides when they are exposed to a moist, oxygen con-
cup will be the main focus for applicability and usefulness taining environment. Therefore, after application the
of adhesion techniques with the aim of reducing the PMMA bone cement does not come in touch directly with
described deficiencies the atoms of the bare metal surface, but rather with the
metal-oxide layer on it. Such oxide layers may allow high
Metal femoral stem initial bond strengths to an acrylic polymer because of
Basics bridge linkage, dipole-dipole interactions, and polariza-
The metal femoral stem is implanted into the femur after tion effects. These high initial bond strengths, however,
the bone has been prepared by rasping within it a conical decrease under the influence of clustered water molecules,
cavity. No adhesive is needed when the implant is fixated which shift the chemical balance that is inside the layer
without cement ("uncemented prosthesis"), since the system responsible for bonding, towards the hydrolyzed
implant surface is covered with a fine mesh of holes (e.g.) state of the interface. The chemical balance, although
that allows bone to grow into the mesh and to tightly highly simplified, can be illustrated as follows:
attach to the prosthesis. However, an adhesive technique
becomes necessary when the prosthesis is to be held in O H2O
place by bone cement ("cemented prosthesis"). Bone Me C MeOH HOC
cement has a methacrylate base, and is used to glue the Kn Me-O-C
metal shaft to the mostly cancellous bone of the femur
cavity walls (exception: in a hip re-operation, the walls are C stands for a carbon atom of the PMMA. After decompo-
no longer cancellous). The interfaces metal stem/bone of sition involving splitting of bonds and addition of the ele-
the femur are mechanically (walking, jumping, etc.) and ments of water, the bonding strength decreases because
chemically (body reaction, temperature, humidity) the hydrolyzed links (right handed side) can only bear
stressed. Whereas the cancellous bone offers many reten- fewer mechanical stresses [14].
tive centers that facilitate a long-life effective anchorage of
the bone cement to the inner walls of the cavity, the metal The water molecules penetrating the PMMA, however, do
surface, however, is much more subject to the risk of de- not only have deteriorating influences, but also healing
bonding. Since the surface of the metallic femur (usually effects. The interface becomes pre-loaded during polymer-
machined out of CoCrMo or TiAl6V4 alloy) is substan- ization [15], and the corresponding shrinkage stresses the
tially smooth, mechanical retention has secondary mean- interface mechanically. This shrinkage is partly compen-
ing and chemical bonding is essential [9,10]. Even if there sated by the materials' expansion due to penetrating
were mechanical interlocking, experience has shown that water. This expansion (1–2%) in part releases the stress
with the moist conditions of the human body, interlock- due to post polymerization shrinkage (6–7%).
ing between a plastic and a metal alone is not sufficient for
a stable bond [11–13]. The use of a silane [28] as a bonding agent does not solve
the problem of unstable bond strength, since the covalent
Water, omnipresent in the body, has an aggressive impact bonds between a silane and the hydroxyl groups -OH of a
on the metal/acrylic joint interface, in particular because metal surface have too poor a hydrolytic stability as well.
of the strong dipole moments of the water molecules. The The silane can realize chemical bondings to the CH2
interface is not protected against the attack of water even groups of the methylmethacrylate [16–19], but not to the
if a gap-free and tight contact between substrate and adhe- metal, since silane coupling agents are designed to stick to
sive could be established. The water molecules can pene- mineral surfaces by siloxane bonds, while a metal surface,
trate into the interface by diffusion, since the bone cement even if oxidized, does not have the active groups that are
as a plastic is permeable; the water molecules are respon- needed. In the presence of a wet atmosphere, the silane
sible for the hydrolytic load of chemical bonding of any coupling agent is not efficient in contact with a bare metal
kind. Water molecules diffuse through any acrylic poly- oxide without mineral enrichment, and hence it is not
mer, and eventually reach that interface which is expected able to stabilize the bonding when high long-term bond
to guarantee the bond between the two materials. Individ- strength is required.
ual water molecules become clustered into a liquid phase.
The chemical bond strength is then challenged. The dan-
Page 3 of 18
Temperature/°C
1050 1100 1150 1200 1250 1300
10 2
Vapor pressure/mbar
Vapor pressure/mbar
1,5
1
0,1
0,5
0,01 0
6 6,5 7 7,5
4
Temperature/10 K/T
Figure
Vapor
ear (onpressure
the
1 right)ofand
silicon
logarithmic
monoxidescale
vs. (on
temperature
the left) on lin-
Vapor pressure of silicon monoxide vs. temperature on lin- Example
Figure 2for epitaxial SiOx film growth
ear (on the right) and logarithmic scale (on the left). Example for epitaxial SiOx film growth. Substrate: slide glass
for microscopy.
Hence, it becomes obvious that the long-term adhesive

strength between silane interlayer/methylmethacrylate conducting films, and for corrosion-protective coatings
and the metal surface can be improved only if the metal [25–27].
surface is modified by an adequate mineral coating
[16,20,21]. To this end, an additional interlayer of silica is The vaporization rate from a hot source into a vacuum
added such that silicon oxide (SiOx) is adhered to the (free surface vaporization) depends on the temperature of
oxides already present on the metal surface [22–24]. the source, the equilibrium vapor pressure of the material
at that temperature, and the pressure in the vacuum cham-
Silicon monoxide is evaporated in a high vacuum atmos- ber. Hence, stable temperatures are mandatory for repro-
phere (p ≈ 0.8...3 * 10-5 mbar) by resistance heating of an ducible film thickness. Silicon monoxide has an
evaporation boat loaded with granulated silicon monox- amorphous crystal structure, and is shipped as a granulate
ide. The inner part of the boat has three compartments. with an average grain sizes of about 0,5 mm (other grain
Two baskets on either end are filled with silicon monox- sizes are also available).
ide granulate. Above the central basket, which is empty,
there is a round chimney through which the vapor stream The purpose of the vacuum is to reduce the gas pressure
passes. A baffle extending down from the cover com- enough so that vaporized atoms have a long mean-free-
pletely surrounds each basket. In addition to the baffles path (at least some decimeters) and so they do not nucle-
around the baskets containing the silicon monoxide, the ate in the vapor to form soot.
cover has a lip that fits snugly and overhangs the boat on
both sides. The ends are sealed as the cover and evapora- Using a shutter, the layer thickness is controlled by the
tion chamber clamp together to form the electrical termi- effective time (product of effective width of slits, number
nations of the evaporator. Thermal shielding surrounds of slits, and number of rotations) the samples are exposed
the evaporator and is attached so that the shields do not to the vapor stream jet. The actual deposition rate is about
produce undesirable cold spots in the evaporation cham- 15 nm/s at a substrate temperature of about 100°C.
bers. After loading with about 3 g of silicon monoxide, the
chamber is electrically heated to 1150± 2°C. The temper- The condensed silica layer is a thin inorganic film of about
ature is measured by means of a thermocouple that is 500 nm thickness, which is tenaciously adherent to the
mounted in one of the baskets that is filled with the sili- substrate. Fig. 2 shows pictures of the epitaxial growth of
con monoxide. At this temperature, silicon monoxide has the layer on glass. It consists of islands that gradually grow
a vapor pressure of about 10-2 mbar (Fig. 1), note that sil- together with evaporation time.
icon monoxide sublimes and does not dissociate signifi-
cantly during sublimation. Silicon monoxide is also The film thickness is measured by the interference fringe
widely used in optical coating technology, for electrically technique. A beam of incident light strikes the silicon
Page 4 of 18
which is a hybrid of silica and of organic groups related to

resins. This surface modifier may theoretically form only
one monolayer, but in practice the treated surface has an
average coverage of 10 to 20 monolayers, corresponding
to a layer thickness of up to 10 µm [28]. The silane func-
tions to chemically modify a surface without contributing
mechanical film properties of its own in the literal sense.
Therefore, the silane has the part of solely a bonding
agent. By a condensation polymerization, the silanol
groups of the hydrolyzed silane form siloxane bonds with
silica surfaces. The methacrylate groups of the silane can
co-polymerize with the monomers of a methacrylate
based polymer (Bis-GMA composite or methylmethacr-
ylate, for example) which results in hydrolysis-resistant
covalent bonds between the coupling agent and resin.
Figure
of
equivalent
about
many)
the 500
surface
with
3 layer
Prosthesis nm)
interference
roughness,
(Modelthickness on®a, smooth
colors
layer
BiContact Aesculap,
thickness
due to SiO
surface
not
Tuttlingen, Therefore, the silane acts as a bridge to bond the metal to
x layering
measurable;
would(because
Ger-
be
Prosthesis (Model BiContact®, Aesculap, Tuttlingen, Ger- the resin with a chain of bonds.
many) with interference colors due to SiOx layering (because
of the surface roughness, layer thickness not measurable; The silane coupling agent is expected primarily to
equivalent layer thickness on a smooth surface would be improve the adhesion between resin and metal in the
about 500 nm). presence of moisture.
O H2O
Me Si MeOH HOSi
K n Me-O-Si
monoxide layer at a certain angle. A portion of the beam
is reflected by the metal surface on which the film is lay- Good bonding stability across the interface requires that
ered, and the remainder of the beam is reflected by the the reaction does not shift too far to the right in the pres-
film. The combined intensity of the net resultant ray at a ence of water. Contrary to the situation for a bare metal
given wavelength is a function of the phase difference surface, the equilibrium state now lies on the left side of
between the two beams at a given wavelength. When the the equation because of the silica modified surface, which
wavelength is continuously varied using a scanning dou- means more stable bonds in the presence of moisture.
ble-beam spectrometer, the resulting spectrum is a contin-
uous series of maxima and minima due to interference. Whereas the siloxane bond between silane and a mineral
From the refractive index, n, of silicon monoxide at the surface or a minerally enriched metallic surface is inor-
wavelengths of interest (0.2 ≤ λ ≤ 1 µm, n ≅ 1,9 ... 1,85), ganic, with a high degree of ionic character, the bond
the distance between two or more minimum wave lengths between the silane coupling agent and the PMMA may be
and the number of fringes between those wavelengths characterized as a bridge of covalent bonds. In the pres-
allow the film thickness to be calculated. Fig. 3 shows an ence of a suitable silane, the double bond of the C atom
example of interference fringes on a femur prosthesis. of the PMMA-CH2-Group opens. After opening, a radical
is available that co-polymerizes with the corresponding
Since the film is only soluble in hydrofluoric acid, it has group of a suitable silane. Note that each kind of plastic
an excellent environmental stability. Its bonding to the needs its individual silane, depending on availability;
surface is thought to be of chemico-mechanical nature by PMMA and BisGMA have a silane in common: an alco-
virtue of the irregularities produced by the sandblasting of holic solution of N-beta-(N-vinylbenzylaminoethyl-
the metal surface prior to the vapor deposition. The small gamma-amino-propyltrimethoxysilane).
silica particles develop a dense, adherent oxide coating
network, which is of a glass like mineral nature, and a The silica-/silane pretreatment can be utilized for metal
chemical constitution SiOx(1≤x≤2). The high vacuum envi- surfaces as well as for ceramic surfaces [9]. At first glance,
ronment, free of pollution, guarantees silica layers with for a ceramic surface containing sufficient silica pre-condi-
reproducible characteristics and of high purity. tioning by a silane should be sufficient. In particular, glass
ceramic materials (crystal phase: feldspar), which are
The joint between the methacrylate based bone cement widely used in the field of dental prosthetics, consist of up
and such a silica layer can be realized by the bifunctional to 70% silica. Note, however, that the surfaces of those
silane bonder (3-Methacryloxypropyltrimethoxysilane), ceramics after sintering are chemically dead and therefore
Page 5 of 18
50
40
Bond strength/M Pa
30
20
10
0
nm
nm
nm
nm
nm
nm
nm
nm
nm
nm
nm
9
49
49
49
49
9
-4
-4
-4
-4
-4
-4
-4
-
-
+/
+/
+/
+/
+/
+/
+/
+/
+/
+/
+/
0
00
00
00
20
30
40
50
60
70
80
90
10
11
12
0 dSiO 30 d thickness/nm
layer 90 d 150 d
Figure
Bond strength
4 vs layer thickness
Bond strength vs layer thickness. Material: unalloyed Titanium samples adhered together with Refobacin®-Palacos®R. Before
adhering together, samples were pre-coated by a protecting layer out of PMMA and BisGMA, similar to the layer protecting
the silica layer on surface of the artificial stem. Without/with hydrolytic load 30 to 150 days; demineralized water, 37°C.
need activation prior to their treatment with silane. More- Experimental results
over, although the coupling agent may have three reactive Experimental investigations of "dependence of bond
silanols per molecule, reactive sites on a mineral surface strength on layer thickness with and without humid load"
can be so spaced that no more than one silanol group per (Figs. 4 and 5), "dependence of bond strength on different
molecule can bond to the surface. The remaining silanol periods of humid load and kind of alloys" (Figs. 6 and 7),
groups may condense with adjacent silanols to form a and "crack concentration near the boundary between
siloxane layer or remain partly uncondensed at the surface bone cement and metal stem" (Fig. 8) will be presented
[28]. For both reasons, silicon monoxide enrichment can below. These studies confirm the long-term hydrolytic sta-
remove the described deficiencies, accomplish additional bility and the efficiency of the layer system. Particularly
"dangling" bonds on the surface, and – enhanced by the significant is how the dramatic reduction of development
obligatory sandblasting treatment prior to PVD layering – of cracks for coated stems underlines the potentiality of
activate the surface. The surfaces of non-siliceous techni- the new technology for cemented orthopedic femoral
cal ceramics such as alumina- or zirconia-oxide can be implants.
modified in a similar manner.
In a wide range of layer thickness the bond strength is
independent of layer thickness, with a tendency to lower
Page 6 of 18
60 50
50 40 43,7
Bond strength/MP a
48,2
Bo nd str ength/M Pa
40 45,2 35,8
30
37,2
30 32,9
29,4 20
20 19,4
20,3
10 12,8 12,0
10 10,4
12,9 12,3 7,6 7,4 8,2 8,5
9,3
7,4 0
0 0d 30d 60d 90d 150d
0d 30d 60d 90d 150d
layered unlayered
layered unlayered
Figure
Bond strength
6 for TiAl6V4 alloy Figure
Bond strength
7 for CoCrMo alloy
Bond strength for TiAl6V4 alloy. Adhesive: Refobacin®-Pala- Bond strength for CoCrMo alloy. Adhesive: Refobacin®-Pala-
cos®R. Without/with hydrolytic load 30 to 150 days; dem- cos®R. Without/with hydrolytic load 30 to 150 days; dem-
ineralized water, 37°C. ineralized water, 37°C.
60
50
cu mulative crack length in %
40
40
Bond strength/M Pa
30
30
20
20
10
10
0
nm
nm
nm
9
49
49
0
84
-4
12
0-
0-
45
0
0 1 2 3 4 5 6 7 8 9 10 11
20
85
0d 30d thickness/nm
layer 90d 150d 360d disk number
Figure
Bond strength
5 vs layer thickness Figurefrequency
Crack
cement
(triangles)
and
8 layer
metal
system
instem
the (TiAl6V4)
boundary region
with (squares)
betweenand
bone
without
Bond strength vs layer thickness. Layer thicknesses grouped Crack frequency in the boundary region between bone
into three classes. Material: unalloyed Titanium samples cement and metal stem (TiAl6V4) with (squares) and without
adhered together with Refobacin®-Palacos®R. Before adher- (triangles) layer system. Disk number 1 to 10: localizations
ing together, samples were pre-coated by a protecting layer along the femur stem from proximal to distal [29].
out of PMMA and BisGMA, similar to the layer protecting the
silica layer on surface of the artificial stem. Without/with
hydrolytic load 30 to 360 days; demineralized water, 37°C.
Page 7 of 18
values and poorer stability under the influence of humid- between bone cement and bone. Below, we describe in
ity beyond a thickness of about 1 µm (Fig. 5). detail the conditioning steps needed to obtain a durable
bond strength between the bonding partners.
The effect of immersion in water at 37°C on adhesive
strength with and without a silica/silane interlayer is Polyethylene as a bonding substrate
shown in detail in Figs. 6 and 7. Without the new coating An essential improvement of bond strength to PE is possi-
layer system (conventionally cemented) high initial adhe- ble employing plasma treatment. A plasma is an excited
sive strengths of about 45 MPa were achieved, but after gas that consists of atoms, molecules, ions, free radicals,
150 days of storage in an humid environment, the adhe- free electrons, and/or metastable species. The use of
sion strength decreased by approximately 75% for the plasma is a common technique to pretreat polymers such
TiAl6V4 alloy/Palacos R cement (Fig. 6) and 80% for the as PE [32]. The plasma may be generated in air (corona
CoCrMo alloy/Palacos R combination (Fig. 7). For the sil- discharge) or under reduced pressure (glow discharge).
ica/silane treated Ti alloy, the adhesive strength fell by The major effects of plasma treatment in the enhancement
23% after 150 days storage. The corresponding number of bond strength are cleaning, crosslinking and oxidation.
for the Co alloy was 46%. As a striking feature it should be Plasma cleaning may be more efficient than solvent
mentioned that the stability for the Ti alloy was much bet- cleaning. The excited species cleaning the surface are
ter than that of the Co alloy [29,30]. expected to have sufficient energy to displace low molec-
ular weight contamination, e.g., water or additives rem-
A characteristic feature in Figs. 6 and 7 is the minimum of nant from processing. Although in most polymers this
the bond strength in the center of the time scale. A plausi- effect is considered as marginal, PE tends to become
ble explanation of this anomaly is given by Hiss [31] and crosslinked. This can be of advantage since it prevents the
Müller [7]. These authors explain that the minimum is development of a weak boundary layer at the interface of
related to the strength minimum of bone cement stored in a joint by decreasing the diffusion of low molecular
water, an effect caused by the competitive effects of water weight species from inside.
diffusing into the cement and of rest monomers diffusing
out of the cement. The former diffusive process is believed Oxidation is probably the most useful feature of plasma
to result in a weakening and the latter process in a treatment. Oxidation may be due to the oxygen part of the
strengthening of cement and hence of bond. A very slow plasma gas or to traces of oxygen being present in the
completion of the silane bonds to its mineral chemical treatment chamber. Polar groups such as unsaturated
partners, which is known to need much time, may be (C=C) and carbonyl (>C=O) groups are introduced into
another reason for the increasing bond strength beyond the surface region of the substrate, improving the wetta-
the center of the time scale. bility of the surface and hence also its adhesion proper-
ties. The improved joining properties are ascribed to the
Because of these effects, we speculate that after a period increased free energy of the polymer surface, especially for
much longer than 150 days, the long term bond strengths PE substrates [33].
again approximate the initial values, as Figs. 6 and 7
demonstrates a continuous increase of bond strength Fig. 9 shows the currently achieved bond strengths with
beyond a storage time of 30 days. and without plasma treatment for medical grade polyeth-
ylene (PE). The treatment results in a bond strength that is
Figs. 8 shows a dramatic reduction of the fissure frequency twice as high than without treatment. The stability under
for the layered stems [29], which is additional proof of the hydrolytic load is also much improved.
superior bond strength of the layered stems.
Bonding to bone
Acetabular component If mechanical interlocking were sufficient for a long-term
Basics retention between adhesive resins and bony substrates,
For a cemented total hip arthroplasty, the acetabular com- questions of chemically bonding could be abandoned.
ponent normally is machined out of ultra high molecular However, questions of wetting might still be important as
weight polyethylene (UHMWPE). PMMA cement is used under the aspect of wetting the bonding partners, resin
to anchor the acetabular component to the bone of the and bone, are incompatible, since resins have hydropho-
acetabulum, just as PMMA cement is used to anchor the bic properties and bone has hydrophilic properties.
femoral stem into the reamed femur.
One has to differentiate between "compact (dense) bone"
With respect to their adherence properties, two bounda- and "cancellous bone". Structures of compact bone are:
ries need to be considered: the boundary between bone osteon with the central Haversian blood vessel canal, lacu-
cement and PE acetabular component, and the boundary nae, canaliculi, and periosteum which covers the outside.
Page 8 of 18
10
with the help of an interlayer system that forms a bridge
between the chemically incompatible resin and bone
9
bonding partners, and which brings the wettability prop-
8
erties (hydrophobic/hydrophilic) of both partners into
7
accommodation [34].
Bond strength/MPa
5 Bone has the following special characteristics that must be

4 taken into account when considering adhesion to it. These
3
characteristics are in part reminiscent of human and
2
bovine tooth dentin. [35,3,36–40]:
1
1. A high proportion of organic substances, especially col-
0
0d 30d 90d 150d
lagen, gives rise to hydrophilic wetting behavior, which is
in contrast to the hydrophobic properties of resin
without plasma treatment with plasma treatment
Figure
(0d)
water,
Bondand37°C)
9with (30d...150d)
PMMA-BisGMA-Bonder
strengths PEhydrolytic
between and surfaces ®-Palacos
load
Refobacin
(sand ®R)adhesive:
(demineralized
blasted, without 2. Blood seepage, which is reminiscent of residual mois-
Bond strengths between PE surfaces (sand blasted, adhesive: ture and dentinal fluid flowing through the tubules
PMMA-BisGMA-Bonder and Refobacin®-Palacos®R) without connecting dentin with the pulp and transportation of
(0d) and with (30d...150d) hydrolytic load (demineralized dentinal fluid from the pulp to the dentin surface
water, 37°C). The samples were plasma treated (20 min,
plasma at 0.5...1 mbar partial pressure of O2). 3. Due to its preparation process, bone is covered with a
layer of debris, e.g., blood, and abraded particles of other
organic and inorganic matter, reminiscent of the smear
layer covering dentin after preparation
Structures of cancellous bone are: trabeculae somewhat Therefore, an adaptive approach is required to firmly
reminiscent to the osteon with lacunae and endosteum. bond a resin in particular bone cement to non-spongy
bone. One may speculate about the feasibility of chemical
Bone is a type of connective tissue made up of cells (oste- bonds between resin and bone. We believe, however, that
oblasts, osteocytes, osteoclasts) suspended in a matrix of chemical bonds play a minor role in comparison with
calcium carbonate, hydroxyapatite, inorganic salts, and micromechanical interlocking to collagen.
collagen fibers. In lamellar bone, the collagen fibers are
laid down in lamellae layers in which all collagen fibers Basically, the micromechanical retention between resin
are oriented in the same direction. Collagen fibers in adja- and compact bone surface is due to resin infiltration into
cent layers are oriented in different directions. The outer the bone surface demineralized by acid etching to a depth
wall of bone shaft is composed of outer circumferential of a few micrometers, thus exposing the collagen fiber net-
lamellae, which completely circle the bone. work without damaging it (Fig. 10). The degree of reten-
tion depends upon the amount of uptake of liquid
Small dots in the bone wall are the nuclei of osteocytes monomers into the interfibrillar spaces that were previ-
located in lacunae (spaces in the bone matrix). The short ously occupied by apatite mineral crystallites. It is thought
tubular structures are called Volkmann's canals. Bone is that the durability of the resin-to bone bond depends
constantly growing and at the same time reshaping. Oste- upon how thoroughly the resin infiltrates these spaces,
oblasts are responsible for producing new bone matrix. whether all of the exposed collagen fibrils are enveloped
Osteocytes are bone cells located in the lacunae and which by resin, and how well the resin is polymerized. During
have characteristic long processes running through the the etching step, the debris layer described above is
bone, being in contact both with other cells and with likewise removed. Both can be done by weak acids such as
blood vessels and nerves. Osteoclasts are responsible for citric, maleic, oxalic, or phosphoric acid. EDTA-Fe-Na
resorption of old bone matrix. (ethylene diamine tetra acetic) can be used as an additive
since it is suitable for the prevention of the denaturation
Micromechanical or chemical resin adhesion to compact of the collagen during and after demineralization. In pre-
bone differs considerably from the simple interlocking of venting denaturation the ferric ion is especially important.
resin to cancellous bone. This is because hydrophobic res- As a further additive glutaric aldehyde can be helpful with
ins do not even wet the hydrophilic bone structures, and protein fixation of collagen fibers.
hence literally no adhesion between resin and substrate
can be expected. Adhesion may nevertheless be achieved
Page 9 of 18
the decalcified layer, resulting in poor quality of the

hybrid layer and low bond strength [41].
The etched bone surface still moist with the collagen

exposed is wetted by amphiphilic monomers.
Amphiphilic molecules generally have a low molecular
weight, which means they are small and mobile. They are
dissolved in water, ethanol, or acetone (e.g.: HEMA
hydroxyethylmethacrylate, GM: glycerylmethacrylate, or
4-META: 4-methacryloxyethyltrimellit). HEMA can help
to straighten collapsed fibers because of its hydrophilic
properties. In addition to hydrophilic molecules, other
monomers supporting film formation (e.g.: UEDMA:
urethane ethylene glycol dimethacrylate), polymerization
and cross-linking (mixtures of BisGMA (bisphenolglyci-
dylmethacrylate) and TEGDMA (triethylen-glycol-
dimethacrylat) (e.g.)) can be included. Amphiphilic mol-
ecules carry at one end a hydrophilic group, which
enables them to penetrate the demineralized bone surface
effectively. This hydrophilic group coupling to the super-
ficial collagen is separated by a spacer from a methacrylate
group on the other end of the molecule. The latter is incor-
porated into the polymeric network within the next bond-
ing step.
The collagen fibers are infiltrated, impregnated, stabi-

lized, and so prevented from collapsing. In the next step,
the stabilized collagen network is infiltrated by a hydro-
phobic monomer that fills the interfibrillar spaces in the
collagen network. For perfect infiltration it is mandatory
Figure
SEM
bone picture
surface
10 of a demineralized (below) vs. untreated (above) that the collagen fibers did not collapse previously. The
SEM picture of a demineralized (below) vs. untreated (above) hydrophobic bonding agent may consist of BisGMA
bone surface. The micromechanical retention between resin (bisphenol glycidyl methacrylate), TEGDMA (triethylene
and compact bone surface may be basically due to resin infil- glycol dimethacrylat), UEDMA (urethane ethylene glycol
tration into the bone surface demineralized by acid etching dimethacrylate), Poly-EGDMA (polyethylene glycol
to a depth of a few micrometers ("hybrid layer"). The investi-
dimethacrylate) or a mixture of these components. For a
gations were done on bone from freshly slaughtered sheep.
firm bonding layer, the infiltrated hydrophobic monomer
in contact with the amphiphilic molecules must be light-
cured, and the bone surface ready for bonding to a bone
cement.
Under continued presence of humidity, after etching the After polymerization, micromechanical retention to bone
collagen network stays suspended, like hair when it floats surface is achieved by the film, which incorporates the
under water. However, if interstitial water is lost, the col- brush-like collagen network. This layer is called the
lagen fibers tend to stick together and subsequently "hybrid layer," which can be regarded as a "composite" of
collapse. Therefore, excessive drying by prolonged air collagen fibers and resin. The penetration steps described
blasting (e.g.) of the bone must be avoided, otherwise a may be limited by the fact that the gaps between exposed
condensed layer of collagen fibers, in which the collagen collagen fibers are very narrow (order of magnitude 100
fibrils stick close together, may be formed, which would nm), and hence the monomers that penetrate the exposed
greatly impede resin penetration into the bone surface. If collagen fibers must have a very low viscosity.
the collagen collapses during any step of the bonding pro-
cedure, the superficial porosity of the bone substrate will Experimental results
be reduced, and many of the sites available for resin In Fig. 11, the achievable bond strengths with and without
infiltration will become lost. The collapsed collagen can the proposed layer system are depicted. The studies were
form a barrier that prevents resin penetration throughout done on bone pieces from freshly slaughtered pigs or
Page 10 of 18
2400 24
Tendono- and Ligamentoplasties
Prosthetic replacement of injured (hyper-flexed, rup-
2000 20 tured) tendons and ligaments presents problems that
have not yet been satisfactorily solved. The hyper-flexed
work of peeling N/m
work of peeling N/m

1600 16 tendon or ligament can be repaired with conventional
surgery. A ruptured tendon or ligament, however, may be
1200 12
surgically repaired by sutering, while the reconstruction or
replacement of an unrepairable tendon or ligament often
800 8
uses autogenous or synthetic materials.
400 4
Autogenous reconstructions imply harvesting prosthetic
0 0 substitutes from other parts of the body of the same indi-
0d 30d 60d 90d 120d 0d: without
BBA
vidual. This process leads to defects and donor site mor-
period of storage bidity. However, because of the long healing periods of
such transplants, the use of synthetic grafts merits
Figure
system
water, 37°C)
(BBA)
11 vs.
BondRefobacin
sive: strengths®in
-Palacos
period ®of
R)hydrolytic
N/m [42] with/without
loadthe
between bone (demineralized
proposed
surfaces layer
(adhe- consideration for such a procedure. Synthetic materials
Bond strengths in N/m [42] between bone surfaces (adhe- have been clinically used for many years. The theoretical
sive: Refobacin®-Palacos®R) with/without the proposed layer advantages of alloplastic grafts are obvious: unlimited
system (BBA) vs. period of hydrolytic load (demineralized availability, intact autogenous structures, minimization of
water, 37°C). The investigations were done on bone from operative time and trauma, technically simpler surgical
freshly slaughtered pigs or sheep. procedure, immediately functional stability, and a shorter
healing process.
Textile constructs for tendon- and ligament replacement

have been employed in orthopedic surgery for many dec-
sheep. Small blocks, 6 mm wide, 12 mm long, and 3 mm ades. First reports by Lange on the implantation of a silk
thick were cut from larger areas of the pelvis, with com- ligament in the knee joint date back to 1903 [43], but
pact bone exposed on those sides on which the bonding proved to be of no use only 3 years after surgery. In the fol-
layer system was to be applied. To assemble one speci- lowing decades the implantation of artificial materials
men, two paired blocks were adhered together (Refo- was sporadically reported, mostly using silk [44]. The
bacin®-Palacos®R as adhesive), the surfaces of both blocks development of plastic materials opened a new area in the
conditioned and pre-layered as described above. The 6 × 1960s. The replacement of the anterior cruciate ligament
12 mm2 contact areas were shielded to the middle of the in dogs was the first application reported [46]. The first
surface (6 mm distance from the edges of the blocks) by a human application was described by Mironova in 1978,
30 µm thick, glossy, and greased aluminum foil. Since the who implanted polyester ligaments in 262 patients over a
bone cement did not adhere to the greased foil, a line of period of 15 years, reporting a 91% success rate [47].
predetermined breaking points was established. These
prepared "sandwiches" were symmetrically extended to The 1970s showed an increased interest in alloplastic lig-
the left and to the right with brass bars of the same cross aments, resulting in commercial products such as the
section (overall length about 30 mm). Note that the rear Proplast® ligament (Vitek-Inc., Houston, Texas; USA)[48]
sides of the two halves of the sandwich had cancellous and the Polyflex® ligament (Richard,, Memphis, Tenn.,
bone exposed so that they could efficiently be fastened to USA). Both products showed poor results and had to be
the brass extensions. With the help of a three point bend- removed in numerous cases due to rupturing and causing
ing arrangement, we were able to measure the work of inflammatory reactions in the joints where they had been
fracture (peeling work) in N/m as a criterion of the quality implanted. Experimental data revealed insufficient
of adherence [42]. The experiment was done with and mechanical properties [49].
without longtime storage in water at 37°C.
In 1977, Jenkins reported on the use of carbon fiber for
Note the different scales in Fig. 11. The right handed scale tendon replacement, which had been in clinical trials
is magnified by a factor of 100, showing that the bond since 1973 [50]. Reports on the application to replace-
strength of pretreated bone is roughly two orders of mag- ment of the cruciate and other ligaments in the knee, and
nitude larger than the bond strength of the unconditioned use in other joints followed [50,51]. After initially prom-
samples. ising results, the carbon fiber ligaments produced severe
problems in clinical application. It was shown that their
poor resistance to cyclic bending forces led to early
Page 11 of 18
ruptures of the fibers, releasing wear particles that could The Trevira® ligament consisting of polyethylenterephtha-
spread throughout the joint, leading to "black joints" and lat has been clinically in use since 1980 [66]. It was first
initiating an inflammatory response. Particles were even used in the cervical spine for stabilizing procedures.
transported to regional lymph nodes [52,53]. The func- Adapted for joint applications, it was implanted in the
tion of the carbon fibers as a scaffold for the ingrowth of knee as a cruciate ligament replacement and as an
connective tissue and for bony ingrowth in the osseous augmentation of autologous transplants. It shows only
canal, which had been anticipated, could not be proven minor wear and inflammatory response in animal trials as
[53]. Also, composite grafting with autologous material or well as in clinical experience. Clinical results are good dur-
the coupling of resorbable polymers to the surface of the ing the first years, while long term studies have not yet
ligament could not outweigh the side effects and compli- been reported. A modified over the top implantation tech-
cations [45]. nique can improve the ligament longevity.
In 1975, Kennedy described the implantation of a poly- The common problem of all alloplastic nonresorbable lig-
propylen ligament (Kennedy-LAD®, 3M, St. Paul, Minn., aments is weakening of the structure due to wear, leading
USA) for the first time [54,55], other reports followed to rupture rates between 5% and 25%per year [67–69].
[56–59] This prosthetic was implanted mostly as Analyzing 117 surgically excised alloplastic ligaments
augmentation for autologous materials, allowing tempo- after failure as anterior cruciate ligament prostheses, Gui-
rary load sharing, while accepting its weakening and rup- doin [70] summarized the major mechanisms that led to
ture with time. All reports stress the good failure as inadequate fiber abrasion resistance against
biocompatibility of polypropylen, butpermanent applica- osseous surfaces, flexural and rotational fatigue of the fib-
tion as ligament prosthesis was not recommended. ers, and loss of integrity of the textile structure due to
unpredictable tissue infiltration during healing.
Polytetrafluoraethylen, (Gore-Tex®, W.F. Gore&Assoc.,
Flagstaff, Ariz., USA)a well established biomaterial used According to Letsch [71], the anchoring mechanism of an
in vascular surgery, in a braided form was also used in lig- alloplastic ligament is one of the crucial points of the sys-
ament replacement surgery. This ligament showed the tem. The maximum load capability of most fixation
best initial load bearing properties of all commercially systems is 10% to 25% of the load capability of the allo-
available alloplastic ligaments. First reports were pub- plastic ligament itself, and therefore is the limiting factor
lished in 1983. Bony ingrowth of the ligament in the of the system. Moreover, the textile structure is weakened
osseous canals was demonstrated. Despite these aspects or damaged by fixation elements like screws or toothed
and promising first clinical reports, the long term clinical staples, leading to loosening of the ligament and addi-
results were disappointing. Frequent ruptures and syno- tional wear [72].
vial reactions within the implanted joints were described
[46,60]. The unsolved problems of alloplastic nonresorbable liga-
ment structures has brought the resorbable ligaments into
A different constructive approach was taken for the focus. Even if the latter provoke an inflammatory
Dacron®-ligament, which was first implanted in the treat- response, they have the advantage that inflammation ends
ment of disruptions of the acromioclavicular joint and in once the resorption is complete. Polydioxanon (PDS®)
tendon replacement. This ligament used a braided 4-fold has been widely used since 1979 [73], as augmentation in
inner part enveloped in a knit cover, which was supposed cruciate ligament surgery, and is available in different con-
to improve tissue ingrowth and lead to an improved structions. Clinical and experimental comparative testing
adaptation of its elastic properties to the human cruciate did not show a significant advantage compared with non
ligament. Also, this ligament showed good initial, augmented transplantation. The decrease in load bearing
however poor long term, results, with a progressive dete- capability of the resorbable ligament during resorption
rioration and high rupture rate [61]. leads to mechanical properties that cannot compete with
those of nonresorbable structures.
Besides the polypropylen ligaments, today only the differ-
ent polyester ligaments play a role in clinical application It becomes clear that, despite the development of a variety
[62]. Examples are the Leeds-Keio® ligament, the Trevira- of synthetic implants and better knowledge of ligament
hochfest® and the Proflex® ligament. biomechanics, there is currently no prosthesis that shows
satisfying long term results. In fact, the life span of liga-
The Leeds-Kejo® ligament was firstly implanted in Japan ment prostheses are rather short. However, this should
1982, also later in the UK. Until 1988 some 20.000 liga- not lead to the conclusion that synthetic grafts are gener-
ments had been implanted. The reported results are few ally unsuitable. Instead, it is evident that there is a need to
and contradictory [63–65]. reconsider the approach and to develop a new generation
Page 12 of 18
of implants and fixations techniques. In particular, the 140–180 N, has been found to be the limiting factor of
method of fixation of ligament prostheses requires atten- most of the ACL replacements. Such forces compares
tion. Currently used fixation techniques allow micro unfavorably with the fixation strength of goat native ACLs
movements of the ligament, which lead to friction against (e.g.), which tolerate loads in excess of 1 kN.
bone, causing wear and implant failure of the entire
prosthesis. In this paper, we discuss two examples describing the use-
fulness of adhesive instead of conventional fixation
The aim of our investigation was to reduce the deficiencies techniques. The adhesive technique is described for a ten-
of the fixation techniques that have been so far applied. don replacement, and may be applied with minor changes
New ideas are proposed for the anchoring of textile struc- for artificial ligaments as well.
tures by using modern adhesive methods that aim for a
more physiological bone-ligament junction [74]. Supraspinatus tendon
Utilizing adhesive methods also means a suitable selec- Basics
tion of the material out of which the artificial tendons and First, we focus on the replacement of the supraspinatus
ligaments are plaited, since not all plastics are appropriate tendon from the rotator cuff group, using alloplastic
for adhesive techniques. Highly desirable are plastics that textile structures. The term "rotator cuff" is used to
fulfill both the clinical necessities and the requirement describe the group of muscles and their tendons in the
that their surface can be effectively conditioned by plasma shoulder that helps control shoulder joint motion. The
treatment. supraspinatus muscle is at the top, the subscapularis in
the front, and the infraspinatus and teres minor are
The fixation technique must result in an anchorage of the behind the shoulder. These muscles attach to the head of
alloplastic prosthesis that is strong enough to prevent slip- the upper arm by way of their tendons. The tendons fuse
page. Moreover, the fixation technique must resemble together, giving rise to the term "cuff." Although each
closely as possible the natural load flux into the bone. The muscle acting alone may produce an isolated rotational
techniques currently utilized lack the tensile characteris- movement of the shoulder, the role they play together is
tics of physiological load flow, and thus they are unable to to help keep the head of the upper-arm ball centered
provide optimum distribution of forces to the bone, since within the socket.
fixation of artificial structures is achieved with staples,
screws, and clips, which of course are accompanied by a In case of a fresh traumatic rupture, the implant is used as
very unfavorable distribution of forces among tendon, fix- an augmentation corresponding to the suture techniques
ation tool, and bone. that are in use today, connecting the ruptured tendon
directly to the bone, where it can heal under stress protec-
As an example, we describe the presently used fixation tion by the implant. After healing, the implant functions
technique for the reconstruction of the anterior cruciate as a permanent augmentation, which is favorable consid-
ligament (ACL) of the knee using a Trevira ligament [75]. ering that the tendon heals with scar formation from tis-
Note that such a ligament is unsuitable for the application sue less mechanically stable than the original tendon.
of adhesive techniques since it consists of many very thin
threads, difficult to prepare for adherence because highly Another application concerns patients with defects in the
viscous adhesives like PMMAs and their modifications are rotator cuff due to degeneration and old rupture. Today,
not able to penetrate threads. For analogous reasons this defect can only be corrected by extensive plastic meth-
plasma treatment is also difficult. The ligament is first ods, transposing autogenous tendon material from other
fixed at the femur. After turning back the windings outside sites [76–78]. Even if – due to biological reasons – a
the over-the-top passage, the ligament is laid flat on the replacement cannot restore function in all cases, it is to be
femur. The femur is marked and a staple is driven in to fix expected that using the novel implant in these situations
the ligament. The end of the ligament is cut until nearly 2 will reduce pain by restoring the joint anatomy [79,80].
cm and placed under the muscles. The final fixation of the Technically, in these cases it will be necessary to bridge the
ligament takes place with a second staple after marking defect by up to three implants, depending on the size of
the tibial cortex. The end of the ligament is also cut to the defect, in order to get a good distribution of forces.
almost 2 cm and placed carefully and flatly under the pes Additionally, it will be necessary to enhance the forma-
anserius. tion of connective tissue between the implant cords to
restore the cuff as a barrier between joint and bursa in
In the long term, the majority of ligament prostheses order to avoid irritation. This can be accomplished either
result in insufficient fixation strength, demonstrating their by local tissue or by additional resorbable implants.
deficient anchorage to the bone. The low fixation
strength, corresponding to fixation failure at forces of
Page 13 of 18
16
14
12
Bond strength/MPa
10
0
0d 30d 90d 150d
without plasma treatment with plasma treatment
Figure
Bond strengths
13 between PVDF surfaces
Bond strengths between PVDF surfaces. Adhesive: self curing
BisGMA. Several kinds of surface treatment (sandblasting and
O2-plasma vs. solely sandblasting) without/with hydrolytic
load (30 ... 150 days (d) in demineralized water, 37°C).
situ
Overall
Figure 12
view of the proposed shoulder fixation element in
Overall view of the proposed shoulder fixation element in
situ. Banjo bolt with alloplastic PVDF tendon adhesively
inserted. Fig. 12 depicts an overall view of the presently proposed
prosthesis as an example. The fixation element [34] con-
sists of a banjo bolt (thread M4...M6 or hollow tapping
screw), the alloplastic PVDF tendon axially inserted. The
screw has been machined out of titanium or a suitable
The alloplastic tendons presently being investigated were titanium alloy (TiAl6V4, e.g.). The inner walls of the screw
braided out of polyvinylidenefluoride (PVDF: common have been PVD layered with a silicon monoxide coating,
brand names: Floraflon, Kynar, Solef). PVDF is a semi- silanized, and finally layered with a very thin film of
crystalline, semi-opaque and white, engineered thermo- PMMA/BisGMA coating, which due to its low viscosity in
plastic that is melt processable. PVDF has good tempera- the unpolymerized state and its hydrophobicity has per-
ture characteristics, and good resistance to general fect wetting properties on a surface enriched by silicate.
chemicals, (though not as good as PTFE's), abrasion, and The PVDF tendon consisting of 8 slackly plaited strands
radiation. It is somewhat stiffer and stronger than most (36 threads bundled into a strand) has been plasma
(being melt-processable) fluoropolymers, which facili- treated and fixed inside the coated banjo bolt by a
tates adhesive techniques for threads. The elongation at BisGMA adhesive, the viscosity of which is adjusted such
break is 50%, the tensile modulus 1 to3 GPa, the density that it can wet each strand or even each thread when the
1.76 g/cm3 and it has a highly dipolar molecule. PVDF adhesive is applied under pressure. The adhesively assem-
radiation resistance (beta, gamma) is good, and therefore bled fixation element (screw and tendon) is allowed to
it may be sterilized by beta-radiation, as is standard for cure overnight.
many orthopedic devices. The desired form is known as
the β phase or Form I, in which the predominantly "head Fig. 13 depicts the bond strengths achievable on PVDF
to tail" polymer chains have an all-trans extended planar samples (cylinders of 6 mm diameter, flat fore-parts in
zig-zag form, with the dipoles of adjacent chains parallel pairs adhered together after conditioning by different
to one another. This pattern is formed from the more plasma treatments).
common α phase (Form II) by mechanical deformation
followed by electrical polarization in a very high electrical For clinical application as replacement or augmentation
field. In practice, both uniaxial and biaxial mechanical of the natural tendon, first a hole in the bone is drilled at
orientations are used. Applications of PVDF include pipes the site marked on the humeral head for tendon reattach-
and fittings, bearings, linings, and vessels (all especially ment. The bolt implant is then screwed into the hole so
for the chemical processing industry), wire insulation and that the top of the implant is at or slightly above the bone
piezo-electric devices. In medical applications, PVDF has surface. The implant must not protrude too much from
been in use as a suture material for years.
Page 14 of 18
160
450
400
350
tendon tensile strength/N
120
upper load F/N

300
250
200
80
150
100
50
40
0 1,0E+05 1,0E+06 1,0E+07
without silica treatment with silica treatment
number of cycles
Figure 14of PVDF tendon and fixation element

Retention Figure amplitude
Fatigue 15 test
Retention of PVDF tendon and fixation element. Pulling at Fatigue amplitude test. Cyclically pulling at fixation element
fixation element (banjo bolt) and PVDF tendon until break. (banjo bolt) and PVDF tendon. Angle between axis of fixation
Diameter of tendon 2,5 mm. Tendon with tight network. element and tendon about 120 degrees. Lower load 10% of
Prosthesis 24 hours soaked in boiling physiological salt solu- upper load, sinusoidal time dependence of load, 3 cycles per
tion at 100°C before being tested. second. Diameter of tendon 2,5 mm. Open triangles: tendon
with tight network, open circles: tendon with loose network.
the surface, otherwise it could give cause to irritation of

the neighboring tissue with inflammation of the bursa smooth power flow between the PVDF tendon and the
(small sac filled with lubricious fluid). The bursa is screw, much smoother than attainable by clamps. Moreo-
located between the tendon and the bone of the humeral ver, a particularly space saving kind of attachment is at
head and cushions the tendon from the bone, thereby hand. Note that it is possible to machine specifically
reducing the friction between the moving structures. adapted screws that allow fixation of the PVDF tendon
under different angles between the axis of the screw and
The free end of the PVDF tendon is sutured to the suprasp- the tendon. Because of the smooth power flow from the
inatus tendon in a way that allows good interconnection tendon into the screw, the risk of injuring and weakening
between tissue and graft so as to accelerate healing and the tendon by notch effects, as they are typical for clamps,
allow early load bearing. After implant surgery, patients is much lower.
should be able to start active exercise with restrained force
within the first week. These advantages could also be helpful replacing the ACL
in knee surgery. As mentioned above, one of the main
Three to nine months are required after implantation to problems of artificial ACL reconstruction is the insuffi-
accomplish bony healing. This process, where bone grows cient fixation stability to the bone. With the proposed
into the implant, is called osseointegration. In the mean- adhesive technique, it could be possible to realize a more
time, the quality of the mechanical screw fixation is stable fixation of the artificial tendon to the bone. In addi-
responsible for the distribution of forces. tion, a more physiological load transfer from the artificial
ligament into the bone seems to be achievable. Although
Experimental results clinical data are missing, experimental work shows
From in vitro experiments we have learned (Fig. 14) that promising results for the use of artificial ACL
the presently proposed implant allows a retention force reconstruction in the near future. Fig. 15 shows fatigue
(measured by axially pulling on ends of fixation element amplitude tests that lead to fatigue failure due to cyclic
and tendon simultaneously) of at least 350 N. This force forces. Such a diagram relates both to material properties
is sufficient to keep the implant stable under body condi- and structural geometry. It requires one specimen to be
tions for at least several months, allowing the body to heal run to rupture in order to provide just one point on the
the tendon by scar-formation and adapting it to the load curve. The frequency of cyclic loading is usually low (pres-
capability required for individual patient activities. These ently 3 cycles per second between maximum and mini-
adhesively fixed tendons have the advantage of a very mum loads) such that one single test may go on for
Page 15 of 18
several days or weeks. A graph of the maximum stress 6. Jasty M, Maloney WJ, Bragdon CR, O'Connor DO, Haire T and Harris
WH: The initiation of failure in cemented femoral compo-
force, F, in newtons (N) vs. cycles to failure (S-N curves) is nents of hip arthroplasties. J Bone Joint Surg (Br) 1991, 73:551-558.
plotted. By successively lowering the maximum stress, 7. Müller K: Mechanische Eigenschaften nicht modifizierter
specimens fatigue-tested without rupture are determined. Knochenzemente auf PMMA-Basis. In: Knochenzement – Werkst-
off, klinische Erfahrungen, Weiterentwicklungen Edited by: Willert HG,
The maximum stress, that does not result in failure can Buchhorn G. Bern, Hans Huber Verlag; 1987:31-44.
thus be determined. This procedure provides important 8. Anthony PP, Gie GA, Ling RSM and Howie CR: Localised endosteal
guidelines for the maximum serving stress that the artifi- bone lysis in relation to the femoral components of
cemented total hip arthroplasties. J Bone Joint Surg 1990,
cial tendon in combination with the fixation element can 72:971-979.
withstand (Fig. 15). 9. Marx R and Fischer H: Werkstück und Verfahren zum Herstel-
len und zum Verwerten des Werkstückes. 1999, DE Patent
19937864 C2:.
Conclusions 10. Verdonschot N and Huiskes HWJ: Cement Debonding Process
When inserting a prosthesis into the human body, not of Total Hip Arthroplasty Stems. Clin Orthop Rel Res 1997,
336:297-307.
only one but several material classes are involved. Up to 11. Crowninshield RD and Tolbert JR: Cement strain measurement
now, clamping and screwing of the structural parts of a surrounding loose and well-fixed femoral component stems.
J Biomed Mater Res 1983, 17:819-828.
prosthesis has been the normal procedure. In the present 12. Willert HG, Brobäck LG, Buchhorn GH, Jensen PH, Köster G, Lang I,
contribution, it is proposed and demonstrated that Ochsner P and Schenk R: Crevice Corrosion of cemented tita-
joining by adhesive techniques can also play an important nium alloy stems in total hip replacements. Clin Orthop 1996,
333:51-75.
and useful part, provided the stability under the condi- 13. Willert HG and Buchhorn GH: The biology of the loosening of
tions of use within the human body is adequately hip implants. In: European Instructional Lectures Courses (Edited by
considered. Within the scope of adhesive techniques, - Jakob RP,. Fulford, P, Horan F) London, EFORT The British Editorial Society
of Bone and Joint Surgery 1999, vol 4:58-82.
resistance to the attack of humidity (besides mechanical 14. Brewis DM, Comyn J and Tegg JL: The durability of some epoxide
load) is mandatory for clinical success. The present work adhesive-bonded joints on exposure to moist warm air. J
Adhesion and Adhesives 1980, 1:35-39.
maintains the thesis that achieving stable bond strengths 15. Müller RT and Schürmann N: Shear strength of the cement
means selecting individually and suitably adapted pre- metal interface – an experimental study. Arch Orthop Trauma
treatments of the material surfaces. Surg 1999, 119:133-138.
16. Herø H, Ruyter IE, Waarli M and Hultquist G: Adhesion of Resins
to Ag-Pd Alloys by Means of the Silicoating Technique. J Dent
Authors' contributions Res 1987, 66:1380-1385.
RM conceived in the study, participated in the design of 17. Ohashi KL, Yerby SA and Dauskardt RH: Effects of a silane adhe-
sion promoter on the fracture and fatigue debond character-
the study and drafted the manuscript. HJE and DCW car- istics of metal/PMMA interfaces. Orlando, Orthopaedic Research
ried out the clinical and experimental studies, MW carried Society 2000.
18. Young PM, Yerby SA, Beaupre GS, Ohashi KL and Goodman SB: The
out experimental work. OP and FUN coordinated the clin- effect of silane coupling agent on the alloy/PMMA interface.
ical part of the work. All authors read and approved the Orlando, Orthopaedic Research Society 2000.
final manuscript. 19. Yerby SA, Paal AF, Young PM, Beaupré GS, Ohashi KL and Goodman
SB: The effect of a silane coupling agent on the bond strength
of bone cement and cobalt-chrome alloy. J Biomed Mater Res
Acknowledgements 2000, 49:127-133.
The project using the Vacuum Vapor Deposition Method to improve the 20. Kern M and Thompson VP: Sandblasting and silica-coating of
dental alloys: volume loss, morphology and changes in the
long-term bonding strength between an orthopaedic metal endoprosthesis surface composition. Dent Mat 1993, 9:155-161.
and PMMA bone cement has been supported by the German Research 21. Musil R and Tiller HJ: Der Kunststoff-Metall-Verbund in der
Community (DFG, project MA 1093/4-1,2). It was realized by close coop- zahnärztlichen Prothetik. Leipzig, VEB J. A. Barth 1988.
eration between the Department of Dental Prosthetics, Section of Dental 22. Beldner W, Niedermeier W, Marx R and Spiekermann H: Silikatis-
ieren als Oberflächenkonditionierung von Metallen für den
Materials, University of Technology Aachen and the Department of Ortho- hydrolysebeständigen Verbund mit Kunststoffen. Quintessenz
paedics, University of Technology Aachen. 1992, 43:103-115.
23. Marx R: Auswahl der Werkstoffe. Adhäsivprothetik Edited by: Ker-
References schbaum T. München, Urbahn & Schwarzenberg; 1995:107-120.
24. Ostkamp V, Vendramini U, Färber H and Marx R: Neue Verfahren
1. Pfeiffer P and Marx R: Temperaturbelastung von Adhäsiv- der Oberflächenkonditionierung und Verbundfestigkeit von
brücken und ihre Auswirkung auf die Verbundfestigkeit der Resinzementen zu Legierungen für die Verblendtechnik und
Klebeverbindung. Schweiz Monatsschr Zahnmed 1989, 99:782-786. Adhäsivrestaurationen. Stomatologie 1997, 94:111-116.
2. Wirtz DC and Niethard FU: Ursachen, Diagnostik und Therapie 25. Bahm EL, Peabody IC and Vedder W: Method of making highly
der aseptischen Hüftendoprothesenlockerung – eine reflective aluminum films. 1968, US Patent 3 498 818:.
Standortbestimmung. Z Orthop 1997, 135:270-280. 26. Haas G: Verfahren zur Verbesserung der Haftfestigkeit von
3. Haller B: Aktueller Stand der Komposit-Dentinhaftung. Zah- metallischen Überzügen. 1957, DE Patent 1 002 584:.
närztl Mitteilungen 1992, 82:86-97. 27. Stetter F and Fritz M: Siliciummonoxid – Herstellung, Eigen-
4. Malchau H and Herberts P: Prognosis of total hip replacement. schaften und sein Einsatz in der Aufdampftechnik. Chemiker-
Surgical and cementing technique in THR: A revision-risk Zeitung 1973, 97:138-145.
study of 134.056 primary operations. Atlanta, 63rd Annual Meet- 28. Plueddemann EP: Silane Coupling Agents. New York, Plenum Press
ing of the AAOS, Atlanta 1996. 1982.
5. Malchau H, Sodermann P and Herberts P: Swedish hip registry: 29. Wirtz DC: Eine neue Beschichtungsmethode für zementierte
results with 20-year follow up validation clinically and Femurschaftimplantate zur hydrolysestabilen Optimierung
radiographically. Orlando, 67th Annual Meeting of the AAOS 2000 . des Metall-Knochenzement-Verbundes. Aachen, Wissenschafts-
verlag Mainz 2002.
Page 16 of 18
30. Fischer H, Wirtz DC, Weber M, Neuss M, Niethard FU and Marx R: 55. Kennedy JC: Experience with polypropylene ligament. Abstract
Improvement of the long-term adhesive strength between book, Can Orthop Assoc Meeting, Ottawa. 1975.
metal stem and polymethylmethacrylate bone cement by a 56. Kennedy JC: Application of prosthetics to anterior cruciate
silica/silane interlayer system. J Biomed Mater Res 2001, ligament reconstruction and repair. Clin Orthop 1983:125-128.
57:413-418. 57. Kennedy JC, Roth JH, Mendenhall HV and Sanford JB: Intraarticular
31. Hiss E: Untersuchungen zum Alterungsverhalten von Kno- replacement in the anterior cruciate ligament-deficient
chenzementen – Eine Langzeitstudie. Knochenzement-Werkstoff, knee. Am J Sports Med 1980, 8:1-8.
klinische Erfahrungen, Weiterentwicklungen Edited by: Willert HG, Buch- 58. McPherson GK, Mendenhall HV, Gibbons DF, Plenk H, Rottmann W,
horn G. Bern, Hans Huber Verlag; 1987:63-66. Sanford JB, Kennedy JC and Roth JH: Experimental mechanical
32. Kinloch AJ: Adhesion and Adhesives. Chapman and Hall, London, and histologic evaluation of the Kennedy ligament augmen-
New York 1987. tation device. Clin Orthop 1985:186-195.
33. Habenicht G: Kleben. Springer, Berlin 1990. 59. Roth JH, Kennedy JC, Lockstadt H, McCallum CL and Cunning LA:
34. Marx R, Fischer H, Niethard FU and Wirtz DC: Knochenhaftver- Polypropylene braid augmented and nonaugmented intraar-
mittler, adhäsives Schichtsystem sowie Verfahren zur Her- ticular anterior cruciate ligament reconstruction. Am J Sports
stellung des Haftvermittlers. 2001, Patent application DE 101 Med 1985, 13:321-336.
46 053.8/101 46 303.0:. 60. Paulos LE, Rosenberg TD, Grewe SR, Tearse DS and Beck CL: The
35. Tinschert J, Wilke M, Esser M and Marx R: Haftfestigkeit und GORE-TEX anterior cruciate ligament prosthesis. A long-
hydrolytische Beständigkeit neuerer Dentinhaftvermittler. term follow up. Am J Sports Med 1992, 20:246-252.
Dtsch Zahnärztl Z 1997, 52:1-4. 61. Barrett GR, Line LL Jr, Shelton WR, Manning JO and Phelps R: The
36. Haller B: Mechanismus und Wirksamkeit von Dacron ligament prosthesis in anterior cruciate ligament
Dentinhaftvermittlern. Dtsch Zahnärztl Z 1994, 49:750-759. reconstruction. A four-year review. Am J Sports Med 1993,
37. Haller B, Hofmann N, Klaiber B and Pfannkuch A: Beständigkeit 21:367-373.
des Komposit-Dentinverbundes bei künstlicher Alterung. 62. Huguet D, Delecrin J, Passuti N and Daculsi G: Ovine anterior cru-
Dtsch Zahnärztl Z 1993, 48:100-104. ciate ligament reconstruction using a synthetic prosthesis
38. Miyasaka K and Nakabayashi N: Combination of EDTA condi- and a collagen inductor. J Mat Science 1997, 8:67-73.
tioner and Phenyl-P/HEMA self-etching primer for bonding 63. Denti M, Arosio A, Monteleone M and Peretti G: Preliminary
to dentin. Dent Mat 1999, 15:153-157. assessment of the anterior cruciate reconstruction with the
39. Nakanuma K, Hayakawa T, Tomita T and Yamazaki M: Effect of the Leeds-Kejo artificial ligament. Am J Knee Surg 1990, 3:181-186.
application of dentin primers and a dentin bonding agent on 64. Macnicol MF, Penny ID and Sheppard L: Early results of the Leeds-
the adhesion between the resin-modified glass-ionomer Keio anterior cruciate ligament replacement. J Bone Joint Surg
cement and dentin. Dent Mat 1998, 14:281-286. Br 1991, 73:377-380.
40. Spencer P, Wang Y, Walker MP, Wieliczka DM and Swafford JR: 65. Emery MA and Rostrup O: repair of the anterior cruciate liga-
Interfacial Chemistry of the Dentin/Adhesive Bond. J Dent Res ment with 8 mm tube Teflon in dogs. Can J Surg 1960,
2000, 79:1458-1463. 4:111-115.
41. Pashley DH, Zhang Y, Agee KA, Rouse CJ, Carvalho RM and Russell 66. Mockwitz J and Contzen H: Alloplastic correction of chronic
CM: Permeability of demineralized dentin to HEMA. Dent Mat knee ligament instability with polyaethyleneterephthalate.
2000, 16:7-14. Aktuelle Probl Chir Orthop 1983, 26:110-115.
42. Marx R, Stoβ Th and Herrmann M: Keramikreparatur – Haften 67. Lobenhoffer P and Tscherne H: Rupture of the anterior cruciate
Reparaturkunststoffe ausreichend? Dtsch Zahnärztl Z 1991, ligament. Current status of treatment. Unfallchirurg 1993,
46:194-196. 96:150-168.
43. Lange F: Über die Verwendung von Seidenfäden. Verh Dtsch Ges 68. Marois Y, Roy R, Vidovszky T, King MW, Belanger AY, Chaput C and
Orthop Chir 1903, 2:10-12. Guidoin R: Histopathological and immunological investiga-
44. Cotton FJ and Morrison GM: Artificial ligaments at the knee. tions of synthetic fibres and structures used in three pros-
New Engl J Med 1934, 210:1331-1334. thetic anterior cruciate ligaments: in vivo study in the rat.
45. Claes L and Neugebauer R: In vivo and in vitro investigation of Biomaterials 1993, 14:255-262.
the long-term behavior and fatigue strength of carbon fiber 69. Olson EJ, Kang JD, Fu FH, Georgescu HI, Mason GC and Evans CH:
ligament replacement. Clin Orthop 1985:99-111. The biochemical and histological effects of artificial ligament
46. Ahlfeld SK, Larson RL and Collins HR: Anterior cruciate recon- wear particles: in vitro and in vivo studies. Am J Sports Med
struction in the chronically unstable knee using an expanded 1988, 16:558-570.
polytetrafluoroethylene (PTFE) prosthetic ligament. Am J 70. Guidoin MF, Marois Y, Bejui J, Poddevin N, King MW and Guidoin R:
Sports Med 1987, 15:326-330. Analysis of retrieved polymer fiber based replacements for
47. Mironova SS: Follow-up results of reconstructing the knee the ACL. Biomaterials 2000, 21:2461-2474.
joint with ligaments of Lavasan. Zentralbl Chir 1978, 103:432-434. 71. Letsch R: Comparative evaluation of different anchoring tech-
48. James SL, Woods GW, Homsy CA, Prewitt JM III and Slocum DB: niques for synthetic cruciate ligaments. A biomechanical and
Cruciate ligament stents in reconstruction of the unstable animal investigation. Knee Surg Sports Traumatol Arthrosc 1994,
knee. A preliminary report. Clin Orthop 1979:90-96. 2:107-117.
49. Grood ES and Noyes FR: Cruciate ligament prosthesis: 72. Kurosaka M, Yoshiya S and Andrish JT: A biomechanical compar-
strength, creep, and fatigue properties. J Bone Joint Surg Am ison of different surgical techniques of graft fixation in ante-
1976, 58:1083-1088. rior cruciate ligament reconstruction. Am J Sports Med 1987,
50. Jenkins DH: The repair of cruciate ligaments with flexible car- 15:225-229.
bon fibre. A longer term study of the induction of new liga- 73. Hudson HC and Glenn JF: New synthetic absorbable suture. J
ments and of the fate of the implanted carbon. J Bone Joint Surg Urol 1979, 122:429-434.
Br 1978, 60B:520-522. 74. Marx R, Fischer H and Erli HJ: Freundes- und Förderkreis des
51. Jenkins DH, Forster IW, McKibbin B and Ralis ZA: Induction of ten- Instituts für Textiltechnik der RWTH Aachen e.V., Aachen:
don and ligament formation by carbon implants. J Bone Joint Verbund eines alloplastischen Textilbandes mit zwei Fixa-
Surg Br 1977, 59:53-57. tionselementen. 2000, Patent application DE 100 23 680.4–
52. Parsons JR, Bhayani S, Alexander H and Weiss AB: Carbon fiber 23:.
debris within the synovial joint. A time-dependent mechani- 75. Yahia L: Ligaments and Ligamentoplasties. Berlin, Springer Verlag
cal and histologic study. Clin Orthop 1985:69-76. 1997.
53. Rushton N, Dandy DJ and Naylor CO: The clinical, arthroscopic 76. Pfahler M, Branner S and Refior HJ: Complete rotator cuff rup-
and histological findings after replacement of the anterior ture – differential surgical techniques and intermediate-
cruciate ligament with carbon-fibre. J Bone Joint Surg Br 1983, term results. Z Orthop Ihre Grenzgeb 1999, 137:295-300.
65:308-309. 77. Warner JJ and Parsons IM: Latissimus dorsi tendon transfer: a
54. Fowler PJ: Kennedy ligament augmentation device for sup- comparative analysis of primary and salvage reconstruction
port of tissue graft in the cruciate deficient knee. Orthop Rev of massive, irreparable rotator cuff tears. J Shoulder Elbow Surg
1985, 14:17-25. 2001, 10:514-521.
Page 17 of 18
78. Zeman CA, Arcand MA, Cantrell JS, Skedros JG and Burkhead WZ Jr:
The rotator cuff-deficient arthritic shoulder: diagnosis and
surgical management. J Am Acad Orthop Surg 1998, 6:337-348.
79. Halder AM, O'Driscoll SW, Heers G, Mura N, Zobitz ME, An KN and
Kreusch-Brinker R: Biomechanical comparison of effects of
supraspinatus tendon detachments, tendon defects, and
muscle retractions. J Bone Joint Surg Am 2002, 84A:780-785.
80. Rickert M, Witzel U, Kolbel R and Georgousis H: Primary strength
of conventional and alternative suture techniques of the
rotator cuff. A biomechanical study. Unfallchirurg 2002,
105:23-30.
Publish with Bio Med Central and every

scientist can read your work free of charge
"BioMed Central will be the most significant development for
disseminating the results of biomedical researc h in our lifetime."
Sir Paul Nurse, Cancer Research UK
Your research papers will be:

available free of charge to the entire biomedical community
peer reviewed and published immediately upon acceptance
cited in PubMed and archived on PubMed Central
yours — you keep the copyright
Submit your manuscript here: BioMedcentral

http://www.biomedcentral.com/info/publishing_adv.asp
Page 18 of 18

2003 - Surface Pretreatments For Medical Application of Adhesion

Uploaded by

2003 - Surface Pretreatments For Medical Application of Adhesion

Uploaded by

BioMedical Engineering OnLine BioMed Central

Review Open Access

University Hospital of the University of Technology, Aachen, Germany

Published: 18 September 2003 Received: 18 March 2003

Introduction physical requirements for successful implantation and

Hence, it becomes obvious that the long-term adhesive

which is a hybrid of silica and of organic groups related to

5 Bone has the following special characteristics that must be

the decalcified layer, resulting in poor quality of the

The etched bone surface still moist with the collagen

The collagen fibers are infiltrated, impregnated, stabi-

work of peeling N/m

Textile constructs for tendon- and ligament replacement

upper load F/N

Figure 14of PVDF tendon and fixation element

the surface, otherwise it could give cause to irritation of

Publish with Bio Med Central and every

Your research papers will be:

Submit your manuscript here: BioMedcentral

You might also like