Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 1 of 7 PagelD 1
`
`IN THE UNITED STATES DISTRICT COURT
`FOR THE WESTERN DISTRICT OF TENNESSEE
`WESTERN DIVISION
`
`CERAMEDIC LLC,
`
`Plaintiff,
`
`Civil Action No.
`
`y.
`
`JURY DEMAND
`
`SMITH & NEPHEW, INC.,
`
`Defendants.
`
`COMPLAINT
`
`CeraMedic LLC ("CeraMedic") hereby asserts claims of patent infringement against
`
`Smith & Nephew, Inc. ("Smith & Nephew"), and alleges as follows:
`
`THE PARTIES
`
`i .
`
`CeraMedic is a Florida limited liability company having a place of business at
`
`2400 Dallas Parkway, Suite 200, Plano, TX 75093.
`
`2.
`
`On information and belief, Smith & Nephew is a Delaware corporation with its
`
`principal place ofbusiness at 1450 Brooks Road, Memphis, TN 38116.
`
`PATENT-IN-SUIT
`
`3.
`
`U.S. Patent No. 6,066,584 ("the '584 patent"), entitled "Sintered AL203 Material,
`
`Process for Its Production and Use of the Material" was lawfully issued on May 23, 2000, with
`
`the original assignee Fraunhofer-Gesellschaft zur Förderung der Angewandten Forschung e.V.,
`
`Germany ("Fraunhofer") . CeraMedic is the owner, through assignment, of the title, interest, and
`
`rights to enforce and collect damages for all past, present, and future infringements of the '584
`
`Exhibit 2324 Page 001
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 2 of 7 PagelD 2
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`patent by the accused products and the use thereof. A copy of the '584 patent is attached as
`
`Exhibit A.
`
`BACKGROUND
`
`4.
`
`Fraunhofer is Europe' s largest application-oriented research organization. Its
`
`research efforts are geared entirely to people' s needs: health, security, communication, energy
`
`and the environment. As a result, the work undertaken by its researchers and developers has a
`
`significant impact on people' s lives. Fraunhofer was honored by Thomson Reuters as one of the
`
`Top 100 Global Innovators in 2013.
`
`5.
`
`Fraunhofer is the assignee of over 1,500 U.s. patents and was the original
`
`assignee of the '584 patent. In early 2014, Fraunhofer assigned ownership of the '584 patent to
`
`CeraMedic.
`
`6.
`
`The '584 patent relates to the field of ceramics and concerns sintered A1203
`
`compositions and methods for the use of such material as medical implants or tool material.
`
`7.
`
`On information and belief, CeramTec GmbH ("CeramTec") developed and
`
`manufactures BIOLOX® Delta, an aluminum oxide matrix composite ceramic comprising
`
`approximately 82% alumina (A1203), 17% zirconia (Zr02), and other trace elements.
`
`8.
`
`BIOLOX® Delta is incorporated into 5mith & Nephew products, such as 5mith
`
`& Nephew BIOLOX® Delta Ceramic Femoral Heads.
`
`9.
`
`5mith & Nephew BIOLOX® Delta Ceramic Femoral Heads can be used in
`
`conjunction with compatible 5mith & Nephew acetabular and femoral stem components for
`
`primary and revision total hip arthroplasty, including at least the SMFTM 5hort Modular Femoral
`
`Hip system, the R3TM Acetabular system, the POLARCUPTM Dual Mobility Hip system, the
`
`Redapt Revision Femoral system, and the AnthologyTM Primary Hip system.
`
`2
`
`Exhibit 2324 Page 002
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 3 of 7 PagelD 3
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`iO.
`
`On information and belief, Smith & Nephew is knowledgeable about the science
`
`behind BIOLOX® Delta material, including its composition, performance characteristics, and
`
`manufacture.
`
`ii.
`
`On information and belief, Smith & Nephew designs, develops, manufactures,
`
`offers for sale, sells, uses, distributes, and markets hip implants, many of which include Smith &
`
`Nephew BIOLOX® Delta Ceramic Femoral Heads. Such hip implants include at least the
`
`SMFTM Short Modular Femoral Hip System, the R3TM Acetabular System, the POLARCUPTM
`
`Dual Mobility Hip System, and the AnthologyTM Primary Hip System.
`
`JURISDICTION AND VENUE
`
`i2.
`
`This Court has subject matterjurisdiction pursuant to 28 U.S.C. § i33i and i338
`
`because this action arises under the patent laws of the United States, including 35 U.S.C. § 27i et
`
`seq.
`
`i3.
`
`This Court has personal jurisdiction over Smith & Nephew because, among other
`
`things, Smith & Nephew' s headquarters are located in Memphis, Tennessee, and because, on
`
`information and belief, Smith & Nephew engages in substantial and ongoing business in this
`
`District.
`
`i4.
`
`On information and belief, Smith & Nephew offers to sell, sells, and distributes its
`
`Smith & Nephew BIOLOX® Delta Ceramic Femoral Heads, which infringe the '584 patent, to
`
`healthcare institutions and/or medical professionals within this District.
`
`i5.
`
`Venue is proper in this judicial district pursuant to 28 U.S.C. § i39i and i400(b)
`
`and in this division pursuant to 28 U.S.C. § i23 and W.D. Tenn. L.R. 3.3(b)(i) and (4).
`
`3
`
`Exhibit 2324 Page 003
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

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`Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 4 of 7 PagelD 4
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`COUNT I - INFRINGEMENT OF THE '584 PATENT
`
`16.
`
`CeraMedic realleges and incorporates by reference each of the preceding
`
`paragraphs.
`
`17.
`
`On information and belief, Smith & Nephew, directly or through the actions of its
`
`employees, divisions, and/or subsidiaries, has infringed and continues to infringe the '584 patent
`
`directly, literally, and/or by equivalents.
`
`18.
`
`On information and belief, Smith & Nephew has infringed and continues to
`
`infringe the ' 5 84 patent literally and/or by equivalents under 35 U.S.C. § 271(a) by, among other
`
`things, importing BIOLOX® Delta ceramics, and making, using, offering for sale, and selling
`
`Smith & Nephew BIOLOX® Delta Ceramic Femoral Heads and/or other products that include
`
`BIOLOX® Delta, individually and/or as part of hip replacement products.
`
`19.
`
`On information and belief, Smith & Nephew has infringed and continues to
`
`infringe the '584 patent literally and/or by equivalents under 35 U.S.C. § 271(g) by, among other
`
`things, importing BIOLOX® Delta ceramics manufactured by CeramTec outside of the United
`
`States , which manufacture by CeramTec would infringe the ' 5 84 patent if it occuned in the
`
`United States.
`
`20.
`
`On information and belief, Smith & Nephew has infringed and continues to
`
`infringe the '584 patent literally and/or by equivalents under 35 U.S.C. § 271(g) by, among other
`
`things, using, offering for sale, and selling Smith & Nephew BIOLOX® Delta Ceramic Femoral
`
`Heads and/or other products that include BIOLOX® Delta, individually and/or as part of hip
`
`replacement products, which products include BIOLOX® Delta manufactured by CeramTec
`
`outside of the United States, which manufacture by CeramTec would infringe the ' 584 patent if
`
`it occurred in the United States.
`
`Exhibit 2324 Page 004
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

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`Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 5 of 7 PagelD 5
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`21.
`
`On information and belief, at least as of the filing of this Complaint, because
`
`Smith & Nephew knew of the '584 patent and knew of the science behind BIOLOX® Delta,
`
`including its manufacture, Smith & Nephew has ignored and/or disregarded that Smith &
`
`Nephew' s actions constituted infringement of a valid patent and Smith & Nephew continues to
`
`ignore and/or disregard an objectively high risk that Smith & Nephew's actions constitute
`
`infringement of a valid patent.
`
`22.
`
`On information and belief, at least as of the filing of this Complaint, Smith &
`
`Nephew' s infringement of the '584 patent is and has been willful and deliberate, and, further,
`
`Smith & Nephew' s continued infringement after the filing of this Complaint shall constitute
`
`willful and deliberate infringement of the ' 584 patent.
`
`DAMAGES AND RELIEF
`
`23.
`
`As a consequence of Smith & Nephew's infringement of the '584 patent,
`
`CeraMedic has been damaged in an amount not yet determined and will suffer additional
`
`ineparable damage unless Smith & Nephew' s infringing acts are enjoined by this Court.
`
`PRAYER FOR RELIEF
`
`WHEREFORE, CeraMedic respectfully requests that the Court enter judgment against
`
`Smith & Nephew:
`
`A.
`
`Determining that Smith & Nephew has infringed and continues to infringe one or
`
`more claims of the '584 patent;
`
`B .
`
`Preliminarily and permanently enjoining Smith & Nephew, its respective officers,
`
`agents, servants, directors, employees, and attorneys, and all persons acting in concert or
`
`participation with it, directly or indirectly, or any of them who receive actual notice of the
`
`judgment, from further infringing the ' 5 84 patent;
`
`5
`
`Exhibit 2324 Page 005
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

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`Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 6 of 7 PagelD 6
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`C.
`
`Ordering Smith & Nephew to account for and pay to CeraMedic all damages
`
`suffered by CeraMedic as a consequence of Smith & Nephew' s infringement of the '584 patent,
`
`together with all pre-judgment and post-judgment interest and costs as fixed by the Court;
`
`D.
`
`Trebling or otherwise increasing CeraMedic' s damages under 35 U.S.C. § 284 on
`
`the grounds that Smith & Nephew' s infringement of the ' 584 patent was deliberate and willful;
`
`E.
`
`Declaring that this case is exceptional and awarding CeraMedic its costs and
`
`reasonable attorneys' fees in accordance with 35 U.S.C. § 285; and
`
`F.
`
`Granting CeraMedic such other and further relief as the Court may deem just and
`
`proper.
`
`JURY DEMAND
`
`Pursuant to Rule 38 of the Federal Rules of Civil Procedure, CeraMedic hereby requests
`
`a trial by jury for all issues so triable.
`
`Dated: July 23, 2014
`
`By:
`
`s/ Adam S. Baldridge
`Adam S. Baldridge (TN BPR No. 023488)
`BAKER, DONELSON, BEARMAN,
`CALDWELL & BERKOWITZ, PC
`165 Madison Avenue
`Suite 2000
`Memphis, TN 38103
`Telephone: (901) 577-2102
`Facsimile: (901) 577-0838
`Email: abaldridge@bakerdonelson.com
`
`Attorneysfor CeraMedic LLC
`
`Exhibit 2324 Page 006
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`Case 2:14-cv-02564 Document 1 Filed 07/23/14 Page 7 of 7 PagelD 7
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`Of Counsel.
`
`John M. Desmarais
`Email: jdesmarais@desmaraisllp.com
`Laurie Stempler
`Email: lstempler@desmaraisllp.com
`Kevin K. McNish
`Email: kmcnish@desmaraisllp.com
`DESMARAIS LLP
`230 Park Avenue
`New York, NY 10169
`Telephone: (212)-351-3400
`Facsimile: (212)-351-3401
`
`Exhibit 2324 Page 007
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`Case 2:14-cv-02564 Document 1-1 Filed 07/23/14 Page 1 of 12 PagelD 8
`
`EXHIBIT A
`
`Exhibit 2324 Page 008
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`United States Patent
`Krell et al.
`
`[19
`
`III III
`
`IID lIDI iDO lIDI IDI IDI IDI ID IIID IID II
`US006066584A
`["1 Patent Number:
`[451 Date of Patent:
`
`6,066,584
`May 23, 2000
`
`[541
`
`SINTERED AL203 MATERIAL, PROCESS
`FOR ITS PRODUCTION AND USE OF THE
`MATERIAL
`
`[751
`
`Inventors: Andreas Krell; Paul Blank, both of
`Dresden, Germany
`
`[581
`
`[561
`
`Field of Search ..................................... 501/127, 153,
`501/128, 132; 51/307, 309; 264/621, 653,
`603, 645
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`[731 Assignee: Fraunhofer-Gesellschaft zur
`Förderung der Angewandten
`Forschung e.V., Germany
`
`[211 Appi. No. :
`
`[221
`
`PCT Filed:
`
`08/727,409
`Apr. 19, 1995
`
`4,052,538 10/1977 Eddy et al ................................ 264/56
`8/1990 Hayashi et al .......................... 501/153
`4,952,537
`5/1992 Kunz et al .............................. 501/127
`5,114,891
`6/1993 Hatanaka et al ........................ 501/153
`5,215,551
`5,261,930 11/1993 Fliedner et al ........................... 51/309
`8/1996 Cornwell et al ........................ 501/153
`5,547,479
`7/1997 Monroe et al .......................... 501/153
`5,645,618
`Primary Examiner-Michael Marcheschi
`Attorney, Agent, or Firm-Medlen & Carroll, LLP
`ABSTRACT
`
`[571
`
`The invention relates to the field of ceramics and concerns
`sintered
`203 compositions produced from corundum pow-
`der and also methods for the use of the invented composi-
`tions as medical implants or tool material. To produce such
`materials, an initially unsintered precursor having a relative
`density of pSS% is produced from a-Al203 powder hay-
`ing defined properties using at least two different dispersing
`methods, this precursor is subsequently subjected to heat
`treatment and sintering.
`
`53 Claims, No Drawings
`
`[861
`
`PCT No.:
`
`§ 371 Date:
`
`PCT/EP95/01474
`Jan. 31, 1997
`Jan. 31, 1997
`§ 102(e) Date:
`[871 PCT Pub. No.: W095/28364
`PCT Pub. Date: Oct. 26, 1995
`Foreign Application Priority Data
`
`[301
`
`European Pat. Off ............... 94106040
`Apr. 19, 1994
`[EPI
`Int. Cl.7 ..................................................... CO4B 35/10
`[511
`[521 U.S. Cl ........................... 501/127; 501/128; 501/132;
`501/153; 264/653; 264/603; 264/645
`
`Exhibit 2324 Page 009
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`6,066,584
`
`SINTERED AL203 MATERIAL, PROCESS
`FOR ITS PRODUCTION AND USE OF THE
`MATERIAL
`
`The invention relates to the field of ceramics and con-
`cerns sintered A'203 materials and processes for their pro-
`duction. The sintered materials can be used as medical
`implants, as wear products, as cutting tools or as abrasives.
`The intensive efforts of recent years aimed at producing
`monolithic sintered Al203 products having grain sizes of
`less than 2 um and improved mechanical properties from
`corundum powder followed essentially two routes:
`use of very fine submicron or nanosize powders,
`addition of substances to lower the temperature required
`for sintering to full density.
`Although the very fine starting materials have the desired
`high sintering activity, owing to their poor densification
`behaviour they at the same time bring with them consider-
`able problems in shaping. The low-cost uniaxial dry pressing
`process, which has hitherto been predominantly employed,
`leads to insufficient green density or to density inhomoge-
`neities in the shaped body and, on sintering, defects which
`reduce the hardness and strength. For these reasons, other
`shaping processes such as cold isostatic pressing, extrusion,
`pressure or centrifugal casting or gel casting are employed.
`An Al203 grain size in the sintered body of 0.8 tm and a
`hardness of HV2O=1920 have been achieved by extrusion of
`ceramic compositions comprising submicron powders and
`sintering at 14000 C. (G. Riedel, et al., Silicates Industriels
`(1989) 1/2,29-35). The powder used here had a mean
`particle size of 0.45 um and a d84 value, which describes the
`width of the coarse particle fraction of the particle size
`distribution, of 1.0 tm.
`In the case of very fine Al203 powders having d50<O.4 tm
`and a d84 value, which describes the width of the coarse
`particle fraction of the particle size distribution, of <0.7 um,
`slip casting has also been successfully used recently (T-5h.
`Yeh et al., J. Am. Ceram. Soc. (1988), pp. 841-844), also in
`combination with the application of pressure (pressure fil-
`tration: F. F. Lange et al., Bull. Am. Ceram. Soc. (1987), pp.
`1498-1504; Vacuum Pressure Filtration: H. Mizuta et al., J.
`Am. Ceram. Soc. (1992), pp. 469-473). As shown, for
`example, by Mizuta et al., these complicated processes
`enable the best mechanical properties up to now for pure
`sintered corundum to be achieved, but according to this prior
`art no Vickers low-load hardnesses of
`2OOO or flexural
`strengths of
`8OO MPa were measured even when hot
`isostatic pressing (HIPping) was employed.
`The usefulness of pressureless casting processes such as
`gel casting or enzyme-controlled coagulation for producing
`pure Al203 ceramics has hitherto been restricted to corun-
`dum powders having mean particle sizes of more than 0.4
`tm (A. C. Young, et al., J. Am. Ceram. Soc. (1991)3,
`612-618), so that the mean grain sizes of the dense sintered
`microstructures produced were always greater than 1.5 um.
`In the example cited, the strengths achieved remained below
`300 MPa.
`The opportunities for improving the mechanical proper-
`ties and the grain fineness of sintered Al203 products
`produced from corundum powder by addition of substances
`which promote sintering are very limited. The temperature
`required for sintering submicron Al203 powders to full
`density is, in particular, reduced to 1200° and less by
`addition of more than 1% of dopants which form liquid
`phases during sintering, but the strengths remain at the level
`usual for traditional sintered corundum, viz, about 400 MPa
`(L. A. Xue et al., J. Am. Ceram. Soc., (1991), pp.
`
`5
`
`15
`
`20
`
`25
`
`30
`
`2
`2011-2013), and the widespread formation of grain bound-
`ary phases brings with it unfavourable high-temperature
`properties.
`Although the relationship between defect structure and
`strength of brittle solids has been well known for a long
`time, most studies are restricted to the purely qualitative
`determination of relevant defect types; even a characteriza-
`tion of only relative defect size distributions (H. E. Exner et
`al., Mater. Sci. Eng. 16 (1974), pp. 231-238) is rare. As
`lo regards the technology dependence of the actually important
`absolute defect frequency per volume or analysed area, as
`studied, for example, for glass (J. R. Matthews et al., J. Am.
`Ceram. Soc. 59 (1976), pp. 304-308), nothing is known for
`A'203 ceramics. There are absolutely no prior studies on the
`effect of such defects on the Vickers hardness.
`In evaluating the hardness of Al203 ceramics thus
`produced, the influence of the test loading used for the
`indenter first has to be taken into account. The Vickers
`hardness of A'203 is, for a single-crystal as well as poly-
`crystalline material, dependent on the load in a complex way
`(A. Krell, Kristall und Technik (1980) 12,1467-74). The
`following material behaviour is typical:
`relatively little load influence at a relatively high test load
`50 N,
`decreasing loading first produces increasing hardness
`values,
`when the test load is reduced further to from <1 to 5 N,
`the hardness can fall again.
`Similar behaviour is found for the Knoop hardness,
`although there are certain systematic differences between the
`numerical results by the Knoop and Vickers methods.
`According to the prior art described below for the sintered
`2°3 products produced by means of known processes
`from corundum powder, the long-established recognition
`that, independently of the respective test load, a grain size
`reduction in the range 2-0.2 tm cannot make possible a
`hardness increase beyond the known upper limits of
`HV102000 (low-load hardness) or HV0.2
`2500
`(microhardness) applies (S. D. Skrovanek et al., J. Am.
`Ceram. Soc. (1979)3/4, 215-216). For the above reasons, a
`comparison of hardness data in the literature is only infor-
`mative when the load dependence of the hardness has been
`examined and the associated test conditions are indicated.
`This is particularly true because the influence of the test load
`varies greatly even within a material group, for example
`sintered corundum, as a function of additives, residual
`porosity and, in particular, the state of the surface. Owing to
`the wide variety of data in the prior art, for which specific
`details are rarely given, the data for the particle size influ-
`ence on the microhardness and low-load hardness or mac-
`rohardness fluctuate within wide limits.
`Microhardness HV (in the range HVO.1-HVO.5, i.e. in the
`range of the possible maximum of the hardness-load curve)
`for single crystals: 2300-2700 (A. G. Evans et al., J. Am.
`Ceram. Soc. (1976)7/8, 371-372)
`for sintered corundum with D2 tm at relative density
`p99%; 2000-2600 (5. D. Skrovanek et al., J. Am.
`Ceram. Soc. (1979)3/4,215-216
`Vickers low-load hardness and macrohardness (test load
`10N)
`for single crystals: 1400-1700 (A. Krell, Kristall und
`Technik (1980)12,1467-1476)
`for sintered corundum with D2 tm at relative density
`p99%: 1650-1850 (A. Krell, Kristall und Technik
`(1980)12,1467-1476)
`for sintered corundum products with D0.45 tm, pro-
`duced by powder technology, at relative density
`
`35
`
`40
`
`45
`
`50
`
`55
`
`60
`
`65
`
`Exhibit 2324 Page 0010
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`6,066,584
`
`3
`p98-98.5%: 1900-2000 (G. Riedel et al., Silicates
`Industriels (1989)1/2, 29-35).
`Specific studies by Skrovanek et al. on the dependence of
`hardness on grain size in virtually fully densified hot-pressed
`sintered corundums having a gradated reduction in grain size
`showed a hardness increase proportional to D112 only down
`to the range 3-4 tm. According to general opinion, this is
`caused by the increasing hindrance of the displacement
`motion in the smaller grains. However, further grain size
`reductions down to 1.7 tm gave no further increase in the
`hardness; the hardness remained constant in this range of
`small grain sizes. This finding has hitherto never been
`contradicted because, according to general opinion a further
`increase in hindrance of the displacement motion with
`decreasing grain size, and therefore increasing hardness, can
`no longer be expected when the grain sizes are of the size
`range of the displacements. Since typical sizes of displace-
`ments (displacement loops) observed in corundum by means
`of transmission electron microscopy are in the micron range,
`the reduction in the grain size effect on the hardness at grain
`sizes of less than 3-4 um was so self-evident that this
`question was not examined in more detail.
`The disadvantage of the sintered Al203 products known
`from the prior art and produced from corundum powder is
`2°3 products having a very low level of
`that no sintered
`defect and very high hardness or high hardness and strength
`are known and able to be produced. Without conclusive
`solutions of the problems having become known up to now,
`current developments are being concentrated internationally
`on two directions which are regarded as promising (T. J.
`Carbone, p. 107 in: L. D. Hart (Editor), "Alumina Chemicals
`Science and Technology Handbook", The Am. Ceram. Soc.,
`Westerville, Ohio, 1990):
`(1) improvement of the sol/gel technologies with addi-
`tions of nuclei (e.g. G. L. Messing and M. Kumagai in
`Bull. Am. Ceram. Soc. 73(1994)88-91),
`( 2) the development and use of powders extremely uni-
`form particle size believed to be ideal ("monosized",
`"uniform-sized") as described by K. Yamada in "Alu-
`mina Chemicals Science and Technology Handbook"
`(Editor L. D.
`Hart, The Am. Ceram. Soc., Westerville, Ohio, 1990, page
`564)
`It is an object of the invention to provide sintered Al203
`materials having improved mechanical properties, in par-
`ticular having high hardness and/or strength.
`The sintered Al203 materials of the invention having an
`Al203 content of from 95 to 100% by volume and a Vickers
`2000 at a test load of from 10 N to
`low-load hardness of
`100 N (HV1 to HV1O) have a relative sintered density of
`98.5%, microstructures having mean grain sizes of
`1.5
`p
`tm and a frequency of inhomogeneities of <50x109 m2.
`The inhomogeneities belong to one or more of the fol-
`lowing categories:
`a) cracks and/or porous regions along the boundaries of
`powder aggregates/powder agglomerates,
`b) nest-like regions in the microstructure having a loos-
`ened structure with many pores,
`c) pores having a diameter exceeding twice the grain size.
`Inhomogeneities of the following category may also be
`taken into account:
`d) grains of >10 tm and/or agglomerates of individual
`grains having an agglomerate size of greater than 10
`um and a diameter which exceeds five times the mean
`grain size.
`0.3 tm may
`In addition, all pores having a diameter of
`be taken into account in the case of the inhomogeneities of
`the category c).
`
`5
`
`15
`
`25
`
`30
`
`20
`
`4
`The frequency of the inhomogeneities is advantageously
`20x109 m2. In contrast, in the case of sintered corundum
`of the prior art, the frequency of the inhomogeneities is more
`than 50x109 m2.
`Advantageously, even sintered microstructures having
`mean grain sizes below 0.8 tm can be obtained using the
`process of the invention.
`The sintered material advantageously has a microstruc-
`turc having a predominantly irregular orientation of the
`lo crystallites.
`In a further embodiment of the invention, importance is
`attached to achieving both a comparatively high hardness
`and a high flexural strength. The additional requirement of
`a high flexural strength in this embodiment requires a
`sintered material which also has a certain size distribution of
`the defects or inhomogeneities as qualifying feature. This in
`turn requires the characterization of the sintered material of
`the invention by means of a dimensionless defect density
`defined as the sum of the squares of the defect sizes per area
`analysed, as was originally introduced for the evaluation of
`microcrack densities (A. Krell et al., J. Mater. Sci. (1987)9,
`3304-08). Here, the defect size employed is the maximum
`recognizable extent of the defect in any direction in the
`analysed plane. In the case of ceramic materials of the prior
`art, the frequency of such inhomogeneities is more than
`30x103. The further embodiment of the invention is char-
`acterized by a content of from 95 to 100% by volume of
`Al203 and a Vickers low-load hardness of
`1750 at a test
`load of from 10 N to 100 N (HV1 to HV1O) and a flexural
`800 MPa, with the sintered material having a
`strength of
`relative sintered density of p 98.5%, a microstructure with
`a mean grain size of
`2 um and a dimensionless defect
`density of <30x103, where the defects belong to one or
`more of the following categories:
`a) cracks and/or porous regions along the boundaries of
`powder aggregates/powder agglomerates,
`b) nest-like regions in the microstructure having a loos-
`ened structure with many pores,
`c) pores having a diameter exceeding twice the mean
`grain size,
`d) grains of >10 tm and/or agglomerates of individual
`grains having an agglomerate size of greater than 10
`um and a diameter which exceeds five times the mean
`grain size.
`The microstructure of the sintered material which com-
`bines high hardness with high flexural strength also advan-
`tageously has a predominantly irregular orientation of the
`crystallites.
`The sintered products of the invention can also contain, in
`50 addition to corundum (a-Al203), up to 5% by volume of
`other substances as long as the abovementioned permissible
`limits of the relative density, the frequency of the inhomo-
`geneities mentioned or the dimensionless defect density are
`still adhered to. The fracture toughness (K1) of the products
`55 of the invention can considerably exceed the level typical for
`sintered corundum, depending on measurement method
`between about 3 and 4.5 MPaVm. However, this is not a
`condition for implementing the invention. For determining
`the fracture toughness, it has to be noted that, in particular,
`the measurement method used has a strong and difficult-to-
`quantify influence on the measured value found, so that
`measured values can frequently not be compared with one
`another.
`A process for producing a sintered Al203 material of the
`invention comprises the following steps:
`a) conversion of an a-Al203 powder having a mean
`particle size d50 of
`0.30 um and a chemical purity of
`
`35
`
`40
`
`45
`
`60
`
`65
`
`Exhibit 2324 Page 0011
`
`CeraMedic Ex. 2324
`CeramTec GmbH v. CeraMedic LLC
`Case IPR2015-01328
`
`

`
`5
`99.9% ofAl2O3 in a liquid into a stable suspension of
`dispersed particles by means of simultaneous and/or
`sequential use of at least two different dispersing
`methods,
`b) production of an unsintered precursor having a relative
`density of p55% by means of shaping,
`c) heat treatment and sintering of the precursor.
`The process of the invention does not require use of very
`expensive powders of uniform ("monosized", "uniform-
`sized") particle size, but rather it can be advantageously
`carried out using a very much cheaper a-Al203 powder
`having the following particle size distribution: d16>O.065
`tm, d50O.3Qum, d84O.45tm. This is a particular advan-
`tage of the invention since it makes possible the production
`of correspondingly high-value sintered materials at lower
`cost than in the case of the prior art. Essential to the success
`of the production process of the invention is the preparation
`of a stable (and particularly homogeneous) suspension of the
`dispersed particles by simultaneous and/or sequential use of
`at least two different dispersing methods.
`Advantageously, the a-Al203 powder used in step a) has
`a specific surface area, determined by the BET method of
`from 10 to 17 m2/g.
`The abovementioned particle size distribution of the
`a'203 starting powder used is of particular importance to
`the success of the invention. Larger mean particle sizes than
`permissible, higher amounts of coarse material (d84 shifted
`to higher values) and correspondingly lower specific surface
`areas reduce the sintering activity, increase the sintering
`temperature required and thus lead to unacceptable coarse
`microstructures. Smaller mean particle sizes or higher
`amounts of very fine material (d16 shifted to lower values)
`cause problems in the subsequent shaping and sintering: the
`resulting reduced green density (i.e. the density of the
`unsintered products) and an increased defect frequency
`likewise require increased sintering temperatures, so that
`coarser sintered products having more inhomogeneities and
`defects are formed. A reduced purity of the powder raw
`material below the value indicated according to the inven-
`tion leads, at least locally, to formation of liquid phases
`during sintering, so that the microstructures produced con-
`tain amorphous grain boundary phases, precipitates,
`micropores and other undesired microdefects. Even when
`amorphous phases cannot be detected, a reduction of the
`powder purity to be adhered to according to the invention
`leads to uncontrollable grain growth processes during sin-
`tering.
`To produce a sintered a-Al203 material in which impor-
`tance is not exclusively attached to a particularly high
`hardness, but in which a high flexural strength is sought at
`the expense of a somewhat reduced hardness, the production
`process of the invention can be modified so as to employ the
`following steps:
`a) conversion of an a-Al203 powder having a particle size
`distribution determined by the parameters d16>O.065
`tm, 0.2 tmd50O.4 tm, 0.45 tmd84O.8 tm and
`a chemical purity of
`99.9% ofAl2O3 in a liquid into
`a stable suspension of dispersed particles by means of
`simultaneous and/or sequential use of at least two
`different dispersing methods,
`b) production of an unsintered precursor having a relative
`density of p55% by means of shaping,
`c) heat treatment and sintering of the precursor.
`The difference between this and the first-mentioned pro-
`cess is that a slightly higher mean particle size and a
`somewhat higher proportion of coarse material may be
`
`40
`
`45
`
`50
`
`55
`
`65
`
`6,066,584
`
`5
`
`permissible. It is thus possible to use an even more mex-
`pensive starting material. Here too, mean particle sizes
`which are larger than permissible, higher proportions of
`coarse material (d84 shifted to higher values) and corre-
`spondingly lower specific surface areas reduce the sintering
`activity, increase the sintering temperature in an unaccept-
`able way and thus lead to microstructures which are too
`coarse-grained to achieve the abovementioned mechanical
`properties. Higher proportions of very fine material (d16
`lo shifted to lower values) and a reduced purity of the powder
`raw material here also cause the same problems as discussed
`above.
`The a-A1203 powder used as starting material in this
`modification of the production process of the invention
`15 advantageously has a specific surface area determined by the
`BET method of 8-17 m2/g.
`The sintering processes used for the purposes of the
`invention can be pressureless or employ pressure (e.g. hot
`pressing or hot isostatic pressing). However, a particular
`20 advantage of the invention is that a-Al203 materials of high
`hardness and/or strength are also obtained when using
`pressureless sintering processes.
`In this context, it may be pointed out that pressureless
`sintering in air compared with hot pressing or hot isostatic
`25 pressing (HIPping) leads, owing to the differences in the
`surrounding atmosphere (in particular the oxygen partial
`pressure), to considerable structural differences which in
`turn alter diffusion coefficients and mechanical, optical and
`electrical properties dependent thereon (S. K. Mohapatra et
`30 al., J. Am. Ceram. Soc. (1978), Issue 3/4, 106-109; 5. K.
`Mohapatra et al., J. Am. Ceram. Soc. (1979), Issue 1/2,
`50-57).
`Hot pressing or hot isostatic pressing are usually carried
`out in a protective gas atmosphere (argon), so that there is a
`reduced oxygen partial pressure and, on the other hand, the
`carbon-containing materials used for the purposes of the
`pressing process result in a CO partial pressure which has a
`reducing action which produces oxygen vacancies as point
`defects distributed over the entire corundum lattice and
`leading to the abovementioned changed properties. Among
`other things, there results a dark grey co