U.S. patent number 3,685,059 [Application Number 05/058,921] was granted by the patent office on 1972-08-22 for prosthetic blood circulation device having a pyrolytic carbon coated blood contacting surface.
This patent grant is currently assigned to Gulf General Atomic Incorporated. Invention is credited to Jack C. Bokros, Willard H. Ellis.
United States Patent |
3,685,059 |
Bokros , et al. |
August 22, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
PROSTHETIC BLOOD CIRCULATION DEVICE HAVING A PYROLYTIC CARBON
COATED BLOOD CONTACTING SURFACE
Abstract
A prosthetic device for implantation in or use with a living
body. A substrate is coated with impermeable pyrolytic carbon which
provides an inert and antithrombogenic outer surface. The
conditions at which the pyrolytic carbon is deposited are
controlled to match the thermal coefficient of expansion of the
pyrolytic carbon to that of the substrate and to provide a strong
carbon which contributes substantial structural strength to the
composite prosthetic device. The carbon is preferably isotropic and
may be doped with a suitable carbide-forming element, such as
silicon, to provide additional structural strength and wear
resistance. Devices having such coatings on the portions coming in
contact with blood are valuable for extracorporeal circulation of
the bloodstream of a human patient.
Inventors: |
Bokros; Jack C. (San Diego,
CA), Ellis; Willard H. (Leucadia, CA) |
Assignee: |
Gulf General Atomic
Incorporated (San Diego, CA)
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Family
ID: |
22019732 |
Appl.
No.: |
05/058,921 |
Filed: |
July 28, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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649811 |
Jun 29, 1967 |
3526005 |
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821080 |
May 1, 1969 |
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Current U.S.
Class: |
623/2.42;
128/899; 427/223 |
Current CPC
Class: |
F04B
9/123 (20130101); F04B 53/124 (20130101); F04B
43/10 (20130101); F04B 53/1002 (20130101); A61M
60/00 (20210101); A61L 33/025 (20130101); F04D
29/2205 (20130101); A61L 27/08 (20130101); A61F
2310/00161 (20130101); A61M 60/268 (20210101); A61M
60/205 (20210101); A61M 60/148 (20210101); A61M
60/894 (20210101) |
Current International
Class: |
A61L
27/00 (20060101); A61L 27/08 (20060101); A61M
1/10 (20060101); A61L 33/02 (20060101); A61L
33/00 (20060101); F04D 29/18 (20060101); F04B
53/12 (20060101); F04B 53/10 (20060101); F04B
9/00 (20060101); F04B 43/10 (20060101); F04B
43/00 (20060101); F04D 29/22 (20060101); F04B
9/123 (20060101); A61F 2/00 (20060101); A61f
001/22 (); A61f 001/24 () |
Field of
Search: |
;3/1,DIG.1,DIG.2,DIG.3
;128/1R,92C,92CA,334 ;117/46CG,46CB,46CC ;23/209.1,209.2,209.4 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
"Construction of a Rigid-Case, Double Ventricle Artificial Heart"
by S. R. Topaz et al., Transactions American Society for Artificial
Internal Organs, Vol. XIII, Apr. 1967, pp. 294-298. .
"The Coating of Intravascular Plastic Prostheses with Coloidal
Graphite" by V. L. Gott et al., Surgery, Vol. 50, No. 2, pp.
382-389, Aug. 1961..
|
Primary Examiner: Gaudet; Richard A.
Assistant Examiner: Frinks; Ronald L.
Parent Case Text
This application is a continuation-in-part of our earlier patent
applications Ser. No. 649,811, filed June 29, 1967 now U.S. Pat.
No. 3,526,005 and Ser. No. 821,080, filed May 1, 1969.
Claims
What is claimed is:
1. A prosthetic device designed for use in the bloodstream
circulation of a human being, which device comprises a substrate
having a shape and size functionally desired, a dense isotropic
pyrolytic carbon coating covering substantially all of the surface
of said substrate which will come in contact with blood, which
pyrolytic carbon has a density of at least about 1.5 grams per cc.,
a BAF between 1.0 and about 1.3 and an apparent crystallite size of
less than about 200A. and means for direct or indirect connection
of the device to the circulatory system of a human being.
2. A prosthetic device in accordance with Claim 1 wherein said
pyrolytic carbon has an apparent crystallite size of about 50A. or
less.
3. A prosthetic device in accordance with Claim 2 wherein said
pyrolytic carbon has an apparent crystallite size of at least about
20A.
4. A prosthetic device in accordance with claim 1 wherein said
pyrolytic carbon coating is at least about 50 microns thick.
5. A prosthetic device in accordance with claim 4 wherein said
substrate has no radius of curvature less than one-quarter inch and
said pyrolytic carbon has a BAF between 1.0 and about 2.0.
6. A prosthetic device in accordance with claim 1 wherein said
pyrolytic carbon has a thermal coefficient of expansion between
about 3 and 6 .times. 10.sup.-.sup.6 /.degree. C. measured at about
20.degree. C.
7. A prosthetic device in accordance with claim 6 wherein said
pyrolytic carbon has a thermal coefficient of expansion plus or
minus about 50 percent of the coefficient of thermal expansion of
said substrate.
8. A prosthetic device in accordance with claim 1 wherein said
pyrolytic carbon contains a carbide additive dispersed therein.
9. A prosthetic device in accordance with claim 8 wherein said
pyrolytic carbon contains up to about 20 weight percent silicon in
the form of silicon carbide.
10. A prosthetic device in accordance with claim 8 wherein said
pyrolytic carbon contains silicon in an amount between about 20 and
10 weight percent in the form of silicon carbide.
11. A prosthetic device in accordance with claim 1 wherein said
substrate has the shape of an element of a blood circulatory assist
device.
12. A prosthetic device in accordance with claim 1 wherein said
substrate has the shape of an element of an artificial heart
valve.
13. A prosthetic device in accordance with claim 1 wherein said
substrate has the shape of a cannula for implantation into the body
of a human being.
14. A prosthetic device in accordance with claim 1 wherein said
substrate is made of graphite.
Description
This invention relates generally to prosthetic devices and more
particularly to prosthetic devices for use within a living body or
in association therewith.
Prosthetic devices, such as intravascular prostheses, have been
used for a number of years, and it is expected that usage of such
devices will increase in the future as medical expertise continues
to improve. One example is the artificial heart valve which is used
fairly extensively today, and more complex circulatory assist
devices, including those which are used extracorporeally, are
currently under development. Artificial kidneys are another class
of prosthetic devices becoming more and more available.
In order to further the development and utilization of prosthetic
devices, the surfaces of these devices which come in contact with
blood and tissue should be completely compatible therewith, whether
the contact be made by implantation within or insertion into the
body or by passage therethrough of blood at locations exterior of
the body. Two of the most common materials for intravascular
prosthesis are metals, for applications where high strength and
good wearability are important, and plastics for applications
wherein flexibility is needed. Metals are thrombogenic and are
subject to corrosion. Plastics, without some treatment, are also
thrombogenic and are subject to degradation. Stainless steel and
tantalum are among the most popular metals used today, whereas
polyethylene, Teflon and the polycarbonates are examples of
plastics considered suitable. None of these materials are
considered to be totally satisfactory for the construction of
prosthetic devices.
It is an object of the present invention to provide improved
prosthetic devices by utilizing improved materials of construction.
Another object is to provide prosthetic devices which are
nonthrombogenic and which will retain this characteristic although
implanted in the body for long periods of time. A further object is
to provide improved prosthetic devices which are compatible with
body tissue, do not cause irritation thereof, and have good
strength and resistance to deterioration when implanted within or
inserted into a living body. Still another object is to provide a
method for making improved prosthetic devices, particularly for
extracorporeal use. One further object is to provide improved parts
for use in extracorporeal apparatus which is exposed to the
circulation of blood.
These and other objects of the invention should be clearly apparent
from the following description of devices embodying various
features of the invention when read in conjunction with the
accompanying drawings, wherein:
FIG. 1 is section view through a circulatory assist device;
FIG. 2 is an enlarged perspective view of a valve disc used in the
device shown in FIG. 1;
FIG. 3 is a sectional view of another type of circulatory assist
device;
FIG. 4 is a perspective view of still another circulatory assist
device;
FIG. 5 is a plan view of yet another type of circulatory assist
device;
FIG. 6 is a sectional view taken along line 6--6 of FIG. 5;
FIG. 7 is a perspective view of an alternative type of impeller
that is employed in the general type of circulatory assist device
shown in FIGS. 5 and 6; and
FIG. 8 is a perspective view of a cannula of the type which might
be inserted into the circulatory system of the human body to
facilitate use of some extracorporeal type of device.
It has been found that prosthetic devices having improved
characteristics can be made by coating suitable substrates of the
desired shape and size with dense pyrolytic carbon. Dense pyrolytic
carbon has been found not only to significantly increase the
strength of the substrate upon which it is coated, but also to
resist wear and deterioration even if implanted within a living
body for long periods of time. While reference is hereinafter
generally made to the use of the prosthetic devices in combination
with a human body, it should also be recognized that the improved
prosthetic devices may be used in other living mammals. For
example, it may be desirable to use pins which include the
indicated pyrolytic carbon coatings for use in repairing or setting
broken bones in horses or dogs. Moreover, for purposes of this
application, the term "prosthetic device" is intended to include
parts for extracorporeal devices which will be in contact with the
bloodstream of a living person.
For use on complex shapes and in order to obtain maximum strength,
it is desirable that the pyrolytic carbon be nearly isotropic.
Anisotropic carbons, though thrombo-resistant, tend to delaminate
when complex shapes are cooled after coating at high temperatures.
Thus, for coating complex shapes (i.e., those having radii of
curvature less than one-quarter inch), the pyrolytic carbon should
have a BAF (Bacon Anisotropy Factor) of not more than about 1.3.
For noncomplex shapes, higher values of BAF up to about 2.0 may be
used, and for flat shapes, pyrolytic carbon having a BAF as high as
about 20 may be used. The BAF is an accepted measure of preferred
orientation of the layer planes in the carbon crystalline
structure. The technique of measurement and a complete explanation
of the scale of measurement is set forth in an article by G. E.
Bacon entitled "A Method for Determining the Degree of Orientation
of Graphite" which appeared in the Journal of Applied Chemistry,
Volume 6, page 477 (1956). For purposes of explanation, it is noted
that 1.0 (the lowest point on the Bacon scale) signifies perfectly
isotropic carbon.
In general, the thickness of the outer pyrolytic carbon coating
should be sufficient to impart the necessary stress and strain
fracture strengths to the particular substrate being coated, and
usually the coating will be at least about 50 microns thick. If a
fairly weak substrate is being employed, for instance one made of
artificial graphite, it may be desirable to provide a thicker
coating of pyrolytic carbon to strengthen the composite prosthetic
device. Moreover, although an outer coating which is substantially
entirely isotropic pyrolytic carbon has adequate structural
strength, the codeposition of silicon or some similar
carbide-forming additive improves the strength and wear resistance
of the carbon coating. As described in more detail hereinafter,
silicon in an amount up to at least about 20 weight percent can be
dispersed in SiC throughout the pyrolytic carbon without detracting
from the desirable thrombo-resistant properties of the pyrolytic
carbon.
The density of the pyrolytic carbon is considered to be an
important feature in determining the additional strength which
pyrolytic carbon coating will provide the substrate. The density is
further important in assuring that the pyrolytic carbon surface
which will be exposed to blood in the environment wherein it will
be used is smooth and substantially impermeable. Such surface
characteristics are believed to reduce the tendency of blood to
coagulate on the surface of the prosthetic device. It is considered
that the pyrolytic carbon should at least have a density of about
1.5 grams per cm.sup.3, and such pyrocarbon is referred to in this
application as dense.
A further characteristic of the carbon which also affects the
strength contribution thereof is the crystallite height or apparent
crystallite size. The apparent crystallite size is herein termed
L.sub.c and can be obtained directly using an X-ray diffractometer.
In this respect
L.sub.c = 0.89 .lambda./.beta. cos.theta.
wherein:
.lambda. is the wave length in A.
.beta. is the half-height (002) line width, and
.theta. is the Bragg angle
Pyrolytic carbon coatings for use in prosthetic devices should have
a crystalline size no greater than about 200A. In general, the
desirable characteristics of pyrolytic carbon for use in prosthetic
devices are greater when the apparent crystallite size is small,
and preferably the apparent crystallite size is between about 20
and about 50A.
Because the substrate material for the prosthetic device will often
be completely encased in pyrolytic carbon, or at least will have
one of its surfaces covered with pyrolytic carbon at a location
that will be in contact with either body tissue or the blood,
choice of the material from which to form the substrate is not of
utmost importance. For example, if the particular prosthetic device
is a pin or a small tube or a portion of a valve, it is likely that
the prosthetic device would be completely covered with pyrolytic
carbon. However, for purposes of this application, the term
prosthetic device is also used to include a part of an apparatus
which is used exterior of the body, for example, as a part of an
auxiliary blood pump or circulatory assist device; and for such a
part, it may be necessary to coat only the surfaces which come in
contact with the blood.
It is considered very important that the substrate material be
compatible with pyrolytic carbon, and more particularly suitable
for use at the process conditions for coating with pyrolytic
carbon. Although it is desirable that the substrate material have
good structural strength to resist possible failure during its end
use, materials which do not have high structural strengths may be
employed by using the pyrolytic carbon deposited thereupon to
supply additional structural strength for the prosthetic
device.
Pyrolytic carbon is, by definition, deposited by the pyrolysis of a
carbon-containing substance so the substrate will be subjected to
the fairly high temperatures necessary for pyrolysis. Generally,
hydrocarbons are employed as the carbon-containing substance to be
pyrolyzed, and temperatures of at least about 1,000.degree. C. are
used. Some examples of the deposition of pyrolytic carbon to
produce coated articles having increased stability under high
temperature and neutron irradiation conditions are set forth in
U.S. Pat. No. 3,298,921. Processes illustrated and described in
this U.S. Pat. employ methane as the source of carbon and utilize
temperatures generally in the range from about 1500 to
2,300.degree. C. Although it may be possible to deposit pyrolytic
carbon having the desired properties with regard to the instant
invention at somewhat lower temperatures by using other
hydrocarbons, for example, propane or butane, generally it is
considered that the substrate material should remain substantially
unaffected by temperatures of at least about 1,000.degree. C., and
preferably by even high temperatures.
Because the substrate is coated at relatively high temperatures and
the prosthetic device will be employed at temperatures usually very
close to ambient, the coefficients of thermal expansion of the
substrate and of the pyrolytic carbon deposited thereupon should be
relatively close to each other if the pyrolytic carbon is to be
deposited directly upon the substrate and a firm bond therebetween
is to be established. Whereas in the aforementioned U.S. Pat. there
is description of the deposition of an intermediate low density
pyrolytic carbon layer, the employment of which might provide
somewhat greater leeway in matching the coefficients of thermal
expansion, it is preferable to deposit the pyrolytic carbon
directly upon the substrate and therefor avoid the necessity for
such an additional intermediate layer. Pyrolytic carbon having the
desired characteristics can be deposited having a thermal
coefficient of expansion in the range of between about 3 and about
6 .times. 10.sup..sup.-6 /.degree. C. measured at 20.degree. C.
Accordingly, substrate materials are chosen which have the
aforementioned stability at high temperatures and which have
thermal coefficients of expansion within or slightly above this
general range, for example up to about 8 .times. 10.sup. .sup.-6
/.degree. C. Examples of suitable substrate materials include
artificial graphite, boron carbide, silicon carbide, tantalum,
molybdenum, tungsten, and various ceramics, such as mullite.
The pyrolytic carbon coating is applied to the substrate using a
suitable apparatus for this purpose. Preferably, an apparatus is
utilized which maintains the substrate in motion while the coating
process is carried out to assure that the coating is uniformly
distributed on the desired surfaces of the substrate. A rotating
drum coater or a vibrating table coater may be employed. When the
substrates to be coated are small enough to be levitated in an
upwardly flowing gas stream, a fluidized bed coater is preferably
used.
As discussed in detail in the aforementioned U.S. Pat., the
characteristics of the carbon which are deposited may be varied by
varying the conditions under which pyrolysis is carried out. For
example, in a fluidized bed coating process wherein a mixture of a
hydrocarbon gas, such as methane, and an inert gas, such as helium
or argon, is used, variance in the volume percent of methane, the
total flow rate of the fluidizing gas stream, and the temperature
at which pyrolysis is carried out all affect the characteristics of
the pyrolytic carbon which is deposited. Control of these various
operational parameters not only allows deposition of pyrolytic
carbon having the desired density, apparent crystallite size, and
isotropy, but also permits the regulation of the desired thermal
coefficient of expansion which the pyrolytic carbon has. This
control also allows one to "grade" a coating in order to provide a
variety of exterior surfaces. For example, a highly oriented
surface coating is believed to provide enhanced thromboresistance
which may be desirable for certain applications. One can deposit a
strong base isotropic pyrocarbon coating, having a BAF of 1.3 or
less, and near the end of the coating operation, one can gradually
change the coating conditions to obtain a highly oriented outer
layer. Using this technique, suitable coatings having outer
surfaces which are highly anisotropic and, for example, are about
25 microns thick, can be conveniently deposited.
Generally, when pyrolytic carbon is deposited directly upon the
surface of the substrate material, the pyrolysis conditions are
controlled so that the pyrolytic carbon which is deposited has a
coefficient of expansion matched to within about plus or minus 50
percent of the substrate material's thermal coefficient of
expansion, and preferably to within about plus or minus 20 percent
thereof. Because pyrolytic carbon has greater strength when placed
in compression than when placed in tension, the thermal coefficient
of expansion of the pyrolytic carbon most preferably is about equal
to or less than that of the substrate. Under these condition, good
adherence to the substrate is established and maintained during the
life of the prosthetic devices.
As previously indicated, the coating may be substantially entirely
pyrolytic carbon, or it may contain a carbide-forming additive,
such as silicon, which has been found to increase the wear
resistance and overall structural strength of the coating. Silicon
in an amount of up to about 20 weight percent, based upon total
weight of silicon plus carbon, may be included without detracting
from the desirable properties of the pyrolytic carbon, and when
silicon is used as an additive, it is generally employed in an
amount between about 10 and 20 weight percent. Examples of other
carbide-forming elements which might be used as additives in
equivalent weight percents include boron, tungsten, tantalum,
niobium, vanadium, molybdenum, aluminum, zirconium, titanium and
hafnium. Generally, such an element would not be used in an amount
greater than 10 atom percent, based upon total atoms of carbon plus
the element.
The carbide-forming additive is codeposited with the pyrolytic
carbon by selecting a volatile compound of the element in question
and supplying this compound to the deposition region. Usually, the
pyrolytic carbon is deposited from a mixture of an inert gas and a
hydrocarbon or the like, and in such an instance, the inert gas is
conveniently employed to carry the volatile compound to the
deposition region. For example, in a fluidized bed coating process,
all or a percentage of the fluidizing gas may be bubbled through a
bath of methyltrichlorosilane or some other suitable volatile
liquid compound. Under the temperature whereat the pyrolysis and
codeposition occurs, the particular element employed is converted
to the carbide form and appears dispersed as a carbide throughout
the resultant product. As previously indicated, the presence of
such a carbide-forming additive does not significantly change the
crystalline structure of the pyrolytic carbon deposited from that
which would be deposited under the same conditions in the absence
of such an additive.
Pyrolytic carbon having the physical properties mentioned
hereinbefore, is considered to be particularly advantageous for
constituting the surface for a prosthetic device because it is
antithrombogenic and is inert to the metabolic processes, enzymes,
and other juices found within living bodies. The antithrombogenic
properties of pyrolytic carbon are believed to be dependent upon
its sterility and the removal of all chemisorbed oxygen therefrom.
Before use, the device may be sterilized, for example, by heating
in a suitable vacuum for about 6 hours at about 130.degree. C. or
by steam autoclaving.
As an alternative to the foregoing sterilization and degassing
techniques, the prosthetic devices can be sterilized in
benzalkonium chloride and then treated with a suitable
anticoagulant which safeguards against the occurrence of
thrombosis. An anticoagulant such as heparin can be used.
Application may be simply made by soaking the prosthetic device in
benzalkonium chloride and then in a heparin solution. A suitable
heparin solution may be prepared by mixing 10 mgs. of heparin per
ml. of saline, saline being a solution of sodium chloride in water.
The sorption of heparin by pyrolytic carbon surfaces purposely
prepared with accessible porosity at the outer surface thereof is
improved by pretreatment with a cationic, surface-active agent such
as an aqueous solution of benzalkonium chloride and heparin. It
should be kept in mind, however, that impermeable pyrolytic carbon
is inherently thromboresistant and prior treatment with heparin is
not essential.
When the prosthetic device is ready for its intended use, for
example as a part of apparatus that will function exterior of a
living body, or perhaps as an implant within a living body to
repair an intravascular defect, known surgical procedures or the
like are employed. A pyrolytic carbon-coated device may be secured
in the proper location within the body, for example, by joining
with Dacron cloth and appropriately suturing using standard
suturing methods.
Illustrated in FIG. 1 of the drawings is a circulatory assist
device in the form of an air operated pump 11. The pump 11 has a
body 13 with an inlet 15 and an outlet 17 for blood and having an
opening 19 for connection to an air line 21. A flexible bladder 23
disposed within the pump body provides a pumping chamber 25 which
is closed at opposite ends by an inlet valve 27 and an outlet valve
29. Each of the valves 27, 29 include doubly convex-shaped disc 31
which is proportioned to close the valve opening therethrough and
which is maintained in association with the opening by a retainer
33. Each disc valve element 31, shown in FIG. 2, is formed with two
identical convex surfaces.
As one example of using this pump 11, the pump inlet 15 is
connected to the left ventricle of the heart. In FIG. 1, the pump
11 is shown with the inlet valve 27 in the open position so that
blood flowing from the left ventricle during systole flows into the
flexible bladder 23. During this filling cycle, the air line 21
connected to the opening 19 is vented. The outlet 17 from the pump
11 is connected to the descending or thoracic aorta. During the
filling cycle, the outlet valve 29 in the pump is closed (as shown)
as the result of the pressure in the aorta. Subsequently, an
external control system supplies air pressure through the opening
19 to the region between the body 13 and the flexible bladder 23.
The application of air pressure squeezes the bladder 23 closing the
inlet valve 27, opening the outlet valve 29 and ejecting the blood
from the bladder into the descending aorta.
It is most important that thrombosis be avoided which might result
in clotting and eventual deterioration in the performance of such a
pump 11. The movable valve discs 31 are one of the locations most
susceptible to thrombosis, and it has been found that by providing
these valve discs with exterior coatings of pyrolytic carbon,
excellent resistance to thrombosis is provided. The discs 31 may be
made of graphite, machined to shape and coated with a 50 -micron
thick coating of dense pyrocarbon. The disc retainers 31 are also
advantageously coated with pyrocarbon. Valves using such discs
continue to open and close well over long periods of use for
pumping human blood.
Shown in FIG. 3 is another type of circulatory assist device or
pump 41 which also utilizes compressed air or the like to power the
pumping operation. The pump includes an outer body 43 having formed
therein a central cylindrical section 45, an upper dish-shaped
section 47 and a lower dish-shaped section 49. A movable pumping
element 51 has the general shape of an inverted funnel. The tubular
stem portion 53 extends through a central opening in the upper body
section 47 and surmounts a concave-shaped portion 55 that is
contoured similarly to the internal surface of the upper pump body
section. A lower inlet 57 is provided in the pump body 43 through
which flow is regulated by a pivoting valve element 59. The movable
pumping element 51 carries another pivoted valve element 59 in the
stem portion 53 thereof which serves as the outlet valve. A
passageway 61 is provided in the upper surface portion 47 of the
pump body which is adapted for connection by a suitable conduit to
a control mechanism (not shown).
The pump 41 may be connected in the same manner as the pump 11
illustrated in FIG. 1. In the position shown, the lower inlet valve
element 59 is in open position and blood is flowing into the
pumping chamber defined generally between the lower dish-shaped
section 49 of the pump body 43 and the movable pumping element 51.
The blood pressure in the aorta maintains the upper valve element
59 in closed position, and the movable pumping element 51
reciprocates upward with the inflow of the blood. During the
filling phase, the region between the upper surface of the movable
pump element 51 and the concave undersurface of the upper pump body
section 47 is vented via the passageway 61. Subsequently, air
pressure is applied through the passageway 61 to drive the movable
pump element 51 downward. This action closes the lower inlet valve,
opens the outlet valve and discharges blood from the pumping
chamber into the descending aorta.
Preferably, all of the internal surfaces of the pump 41 which come
in contact with blood are coated with pyrolytic carbon. In this
respect, the internal surfaces of the sections 45 and 49 of the
pump body 43 would be so coated along with the inner surface of the
inlet 57. The entire inner surface of the movable pumping element
51 should also be coated. Likewise, both of the pivoting valve
elements 59 are completely coated with a layer of pyrolytic carbon.
In addition to being thromboresistant, the pyrolytic carbon
provides an excellent bearing surface and exhibits good wear
characteristics in the region of the cylindrical wall section 45
where there is sliding contact with the peripheral edge of the
reciprocating pumping element 51. Such a pump 41 is capable of
continuous operation without the development of blood clotting.
Illustrated in FIG. 4 is another type of circulatory assist device
in the form of a piston-type pump 71. The pump has an outer body or
casing 73 and contains a sleeve 75 that serves as a cylinder wall
that is in sliding contact with a floating piston 77 which has the
shape of a right circular cylinder. The piston 77 slides freely in
the sleeve 75, and its movement is controlled via an opening 79 in
the lower surface of the casing 75 to which a conduit is connected,
as the case of the pumps 11 and 41. The casing 73 forms a pumping
chamber 81 above the upper face of the piston 77 and contains,
side-by-side, an inlet 83 and an outlet 85, each of which are
provided with ball valves 87 and 89, respectively. Each valve
includes a movable spheroid 91 and a retaining cage 93.
The operation of the pump 71 is similar to the operation previously
described, and the pump is illustrated near the end of the pumping
phase, just before the filling phase begins. The floating piston 77
moves downward when blood is flowing into the pumping chamber 81
through the inlet valve opening, and the blood pressure in the
aorta maintains the outlet ball 91 in the closed position. Upon
completion of the filling phase, air pressure is applied to the
lower opening 79, forcing the floating piston 77 upward, closing
the inlet valve 87 and pumping the blood from the pumping chamber
81 through the outlet valve 89 into the descending aorta.
It has been found that this piston blood pump 71 has substantially
improved resistance to blood clotting if the sleeve 75 and the
piston 77 are coated with an exterior layer of pyrolytic carbon.
Moreover, the movable ball valve spheroids 91 are also
advantageously made from a suitable substrate, such as graphite,
and coated with pyrolytic carbon. Depending upon the material from
which the retaining members 93 are made, these members are also
provided with an outer coating of pyrolytic carbon that prevents
clotting thereadjacent over a long duration of operation.
Shown in FIGS. 5 and 6 in a centrifugal type of circulatory assist
device or pump 101 having a two-piece housing wherein a rotor 103
revolves. An upper portion 105 of the housing flares outward from a
central inlet opening 107 to present a smooth flaring undersurface
which may be described as being generally bell-shaped. A lower
housing portion 109 mates with the upper portion 105 and contains a
flat circular wall 111 having an upstanding short peripheral wall
113.
The rotor 103 consists of three separate sections 115, 117 and 119
each having progressively slightly greater curvature than the
underside of the upper housing portion 105 which is interconnected
by pins 121. The lowermost rotor section 119 is linked by suitable
struts 123 to a central shaft 125 which extends downward through a
drilled hole in the circular wall 111 to facilitate connection to
an electric motor 127. The lower portion 109 of the two-piece
housing contains a tangentially located outlet 129 in the
peripheral wall 113. Spacing between the three rotor sections is
such as to provide a viscous drag on the blood and impart
centrifugal motion to it which propels it outward and through
outlet 129. Accordingly, revolution of the three-piece rotor 103 by
the electric motor 127 causes blood to be drawn into the inlet
opening 107 and centrifugally discharged through the tangential
outlet 129.
It has been found that the performance of the centrifugal pump 101
is substantially improved by the avoidance of clotting as a result
of coating the components that come in contact with blood with a
layer of pyrolytic carbon. In this respect, the interior surface of
the pumping cavity formed by the two-piece housing is coated with
pyrolytic carbon. Moreover, all of the surfaces of the
three-segment rotor 103 and the connecting pins 121 and struts 123
are also coated.
Shown in FIG. 7 is an alternative design of a rotor 131 which is
also employed in a centrifugal circulatory assist device of the
general type as that shown in FIGS. 5 and 6. The rotor 131 is
affixed to a drive shaft 133 attached to it and has an upper
conical portion 135 from which extend six triangular-shaped blades
137. The entire rotor and any portion of the shaft which extends
into the pumping cavity are preferably coated as a unit with a
layer of pyrolytic carbon in the manner hereinbefore described.
Illustrated in FIG. 8 is a cannula 141 of tee shape. The cannula
141 is designed for implantation in the body of a patient who will
periodically be submitted to artificial kidney treatments. For
example, the long straight run 143 of the tee may be spliced into
the vein of a patient while the short stem section 145 of the tee
extends upward to the surface of the skin. If pyrolytic carbon is
used to completely coat the cannula 141, it can be implanted as a
permanent installation inasmuch as clotting is avoided. Normally,
the short stem section 145 of the tee is closed by a suitable plug,
and the blood flows straight through the run of the tee. When, for
example, dialysis is desired, blood is removed from an artery using
a similar tee and is returned to the vein via the stem 145. The
ability of a pyrolytic carbon coating to permit a permanent
installation of this type is of substantial advantage to a patient
who must frequently be subjected to such treatments.
The following examples illustrate several coating processes for
producing prosthetic devices having pyrolytic carbon surfaces
exhibiting various advantages of the invention. Although these
examples include the best modes presently contemplated by the
inventors for carrying out their invention, it should be understood
that these examples are only illustrative and do not constitute
limitations upon the invention which is defined by the claims
appearing at the end of this specification.
EXAMPLE I
Short tubes are constructed of artificial graphite each having a
length of 9mm., an internal diameter of 7mm. and a wall thickness
of 0.5mm. The artificial graphite employed has a coefficient of
thermal expansion of about 4 .times. 10.sup.-.sup.6 /.degree. C.
when measured at 50.degree. C. The short tubes are coated with
pyrolytic carbon using a fluidized bed coating apparatus.
The fluidized bed apparatus includes a reaction tube having a
diameter of about 3.8 cm. that is heated to a temperature of about
1,350.degree. C. A flow of helium gas sufficient to levitate the
relatively small tubes is maintained upward through the apparatus.
The small short tubes are coated together with a charge of
zirconium dioxide particles of about 50 grams, which particles have
diameters in the range of about 150 to 250 microns. The particles
are added along with the short tubes to provide a deposition
surface area of the desired amount, relative to the size of the
region of the reaction tube wherein pyrolysis occurs, inasmuch as
the relative amount of available surface area is another factor
which influences the physical characteristics of the resultant
pyrolytic carbon.
When the temperature of the articles which are levitated within the
reaction tube reaches about 1350.degree. C., propane is admixed
with the helium to provide an upwardly flowing gas stream having a
total flow rate of about 6,000 cc. per minute and having a partial
pressure of propane of about 0.4 (total pressure one atmosphere).
The propane decomposes under these conditions and deposits a dense
isotropic pyrolytic carbon coating upon all of the articles in the
fluidized bed. Under these coating conditions, the carbon
deposition rate is about 5 microns per minute. The propane gas flow
is continued until an isotropic pyrolytic carbon coating about 200
microns thick is deposited on the outside of the tubes. At this
time, the propane gas flow is terminated, and the coated articles
are cooled fairly slowly in the helium gas and then removed from
the reaction tube coating apparatus.
The short tubes are examined and tested. The thickness of the
pyrolytic carbon coating on the interior of the tube measures about
200 microns. The density of the isotropic carbon uniformly is found
to be about 2.0 grams per cm..sup.3. The BAF is found to be about
1.1. The apparent crystallite size is measured and found to be
about 30 to 40A. Mechanical tests of the coated short tubes are
made to determine their strength in comparison to additional
uncoated graphite tubes. The crushing load of the uncoated graphite
tubes, loaded parallel to the diameter, is found to be about 4
pounds. The crushing load of the coated tubes is about 25 pounds,
about 6 times higher. Another of the coated tubes is sterilized by
heating to about 1000.degree.C. in a vacuum and then is soaked for
15 minutes in a dilute solution of benzalkonium chloride (1 part by
1,000 parts water). The coated tube is then removed, rinsed and
then soaked for 15 minutes in a heparin solution prepared at a
level of 10 mgs. of heparin per ml. of saline. After removal, the
tube is rinsed ten times with saline and is then tested with blood.
After contact with blood for about 24 hours, no sign of clotting is
shown, and clotting normally occurs within a matter of minutes. The
pyrolytic carbon-coated, graphite substrate articles are considered
to be excellently acceptable for use as prosthetic devices within
the body of human beings.
EXAMPLE II
A number of short tubes having the same dimensions as those used in
Example I but made of tantalum are provided. Tantalum has a thermal
coefficient of expansion of about 6.5 .times. 10.sup.-.sup.6
/.degree. C., measured at 20.degree. C. The short tubes are coated
in the fluidized bed reaction tube employed in Example I. In order
to match the pyrolytic carbon coefficient of thermal expansion to
that of the tantalum substrate, a coating temperature of
1,600.degree. C. is employed using a 15 percent propane -- 85
percent helium gas stream having a total flow rate of about 6,000
cc. per minute. The short tubes are levitated together with a
similar 50 gram charge of particles of zirconium dioxide at
atmospheric pressure. Deposition of pyrolytic carbon is carried out
for about 20 minutes, after which period a layer of isotropic
pyrolytic carbon about 150 microns thick coats the outer surface of
each of the tubes. At the end of this time the propane flow is
discontinued, and the coated tubes are cooled and removed from the
reaction tube.
Examination and testing shows that the density of the isotropic
pyrolytic carbon deposited is about 1.6 grams per cm..sup.3. The
BAF is about 1.0. The apparent crystallite size is between about 50
to 60A. The thermal coefficient of expansion of the pyrolytic
carbon measures about 5 .times. 10.sup.-.sup.6 /.degree. C. at
about 20.degree. C. Mechanical testing of the coated tubes shows
that the strength and wearability is acceptable and that the
coating is firmly affixed to the substrate.
One of the coated short tubes is sterilized and treated as in
Example I excepting that the treatment with benzalkonium chloride
and heparin is omitted. The tube is tested with blood, and there is
no sign of clotting after contact therewith for 24 hours. The
carbon-coated tantalum articles are considered to be excellently
acceptable for use as a part of a prosthetic device for
implantation within a human body.
EXAMPLE III
A number of short tubes having the same dimensions as those used in
Example I but made of tungsten are provided. Tungsten has a thermal
coefficient of expansion of about 4.4 .times. 10.sup.-.sup.6
/.degree. C., measured at 27.degree. C. The short tubes are coated
in the fluidized bed reaction tube employed in Example I. In order
to match the pyrolytic carbon coefficient of thermal expansion to
that of the tungsten substrate, a coating temperature of
1600.degree.C. is employed using a 15 percent propane -- 85 percent
helium gas stream having a total flow rate of about 6,000cc. per
minute. The short tubes are levitated together with a similar 50
gram charge of particles of zirconium dioxide. Deposition of
pyrolytic carbon is continued for about 20 minutes, at which time a
layer of isotropic pyrolytic carbon about 150 microns thick coats
the outer surface of each of the tubes. The propane flow is
discontinued, and the coated tubes are cooled and removed from the
reaction tube.
Examination and testing shows that the density of the isotropic
pyrolytic carbon deposited is about 1.6 grams per cc. The BAF is
about 1.0. The apparent crystallite size is between about 50 to
60A. The thermal coefficient of expansion of the pyrolytic carbon
measures about 5 .times. 10.sup.-.sup.6 /.degree. C. at about
20.degree. C. Mechanical testing of the coated tubes shows that the
strength and wearability is acceptable and that the coating is
firmly affixed to the substrate.
One of the coated short tubes is sterilized and treated as in
Example I with benzalkonium chloride and heparin and tested with
blood. There is no sign of clotting after contact therewith for 24
hours. The carbon-coated tungsten articles are considered to be
excellently acceptable for use as a part of a prosthetic device for
implantation within a human body.
EXAMPLE IV
A number of short tubes having the same dimensions as those used in
Example I but made of molybdenum are provided. Molybdenum has a
thermal coefficient of expansion of about 5.3 .times.
10.sup.-.sup.6 /.degree. C., measured at 20.degree. C. The short
tubes are coated in the fluidized bed reaction tube employed in
Example I. In order to match the pyrolytic carbon coefficient of
thermal expansion to that of the molybdenum substrate, a coating
temperature of 1,350.degree. C. is employed using a 30 percent
propane -- 70 percent helium gas stream having a total flow rate of
about 5,500cc. per minute. The short tubes are levitated together
with a similar 50 gram charge of particles of zirconium dioxide.
Deposition of pyrolytic carbon occurs, and after about 30 minutes a
layer of isotropic pyrolytic carbon about 150 microns thick coats
the outer surface of each of the tubes. At the end of this time,
the propane flow is discontinued, and the coated tubes are cooled
and removed from the reaction tube.
Examination and testing shows that the density of the isotropic
pyrolytic carbon deposited is about 2.0 grams per cm..sup.3. The
BAF is about 1.1. The apparent crystallite size is between about 30
and 40A. The thermal coefficient of expansion of the pyrolytic
carbon measures about 5 .times. 10.sup.-.sup.6 /.degree. C. at
about 20.degree. C. Mechanical testing of the coated tubes shows
that the strength and wearability is acceptable and that the
pyrolytic carbon coating is firmly bonded to the substrate.
One of the coated short tubes is polished, sterilized and treated
as in Example I with benzalkonium chloride and heparin and is
tested with blood. There is no sign of clotting after contact
therewith for 24 hours. The carbon-coated molybdenum short tubes
are considered to be excellently acceptable for use as a part of a
prosthetic device for implantation within a human body.
EXAMPLE V
A number of graphite tubes having the same characteristics and
dimensions as those used in Example I are introduced into a
reaction tube which is about 6.3 cm. in diameter, together with an
ancillary charge of 100 grams of zirconium oxide spheroids having
an average particle size of about 400 microns. A fluidizing flow of
helium is fed upward through the reaction tube as the temperature
of the small tubes and particles is raised to about 1,350.degree.C.
When this temperature is reached, propane is admixed with the
helium to provide a total gas flow of about 8,000 cc. per minute,
having a partial pressure of propane of about 0.4 atm.(total
pressure of 1 atm.). All of the helium is bubbled through a bath of
methyltrichlorosilane at about room temperature. The propane and
the methyltrichlorosilane pyrolyze to deposit a mixture of
isotropic carbon and silicon carbide on the small tubes, and the
coating process is continued until a coating about 12 mils (300
microns) thick is obtained, a time of about an hour.
The resultant coated tubes are allowed to cool to ambient
temperature, and they are then removed from the reaction tube.
Examination of the isotropic carbon-silicon carbide coating shows
that it has a coefficient of thermal expansion of about 6 .times.
10.sup.-.sup.6 /.degree. C. and a density of 2 grams per cm.sup.3.
The coating contains about 10 weight percent silicon (based upon
total weight of silicon plus carbon) in the form of silicon
carbide. The isotropic carbon has a BAF of about 1.1 and an
apparent crystallite size of about 35A. Mechanical testing of the
coated tubes shows that the strength and wearability are fully
acceptable and that there is a firm bond between the coating and
the graphite substrate.
One of the coated tubes is polished, sterilized and treated as in
Example I, using benzalkonium chloride and heparin, and it is then
tested with blood. There is no sign of clotting after contact with
blood for 24 hours. The tubes which are coated with pyrolytic
carbon containing the silicon carbide additive are considered to be
excellently acceptable for use as a part of a prosthetic device and
suitable for implantation within a human body.
Although the examples have been particularly directed to the
coating and use of short tubes, it should be understood hat the
examples are provided for the purpose of illustration. Any suitably
shaped elements including all of those shown in the drawings can be
coated to provide prosthetic devices of the improved design.
Deposition of pyrolytic carbon in a fluidized bed process is
excellently suited for the smooth coating of even very
complex-shaped elements. The improved prosthetic devices have
excellent resistance to degradation in a living body and are
likewise eminently well suited for parts in circulatory assist
devices that handle the bloodstream of a living human being.
Various of the features of the invention are set forth in the
claims that follow.
* * * * *