|Publication number||US20100240517 A1|
|Application number||US 11/430,013|
|Publication date||Sep 23, 2010|
|Priority date||May 9, 2006|
|Also published as||US7803732|
|Publication number||11430013, 430013, US 2010/0240517 A1, US 2010/240517 A1, US 20100240517 A1, US 20100240517A1, US 2010240517 A1, US 2010240517A1, US-A1-20100240517, US-A1-2010240517, US2010/0240517A1, US2010/240517A1, US20100240517 A1, US20100240517A1, US2010240517 A1, US2010240517A1|
|Inventors||Daniel Ashkin, Richard Palicka|
|Original Assignee||BAE Systems Advanced Ceramics, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Classifications (16), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The present invention relates to compositions for improved ceramic armor. Dense silicon carbide ceramics have been shown to be an effective means to protect against a wide variety of ballistic threats because of their combination of high hardness, strength and stiffness with low bulk density and favorable pulverization characteristics upon impact. Dense silicon carbide is typically produced using the following method steps:
Silicon carbide is a covalently bonded ceramic having low self-diffusion coefficients. To increase diffusion and facilitate densification, sintering aids are added in amounts generally less than 5 volume percent. For silicon carbide, the first additive used for densification was Al2O3 and the method for densification was hot pressing. This was developed in the 1950s as reported by the Journal of the American Ceramic Society, Volume 39, pp. 386-89 (1956) in the article by Alliegro et al. titled “Pressure-Sintered Silicon Carbide.” Effective use of Al2O3 was also reported by the Journal of Material Science, Vol. 10, pp. 314-320 in the article by F. F. Lange titled “Hot-Pressing Behavior of SiC Powders with Additions of Alumina,” and was shown by Lange to be due to liquid phase sintering. In 1970s and 1980s, pressureless sintering was developed by using compounds based on elements such as Boron (B), (S. Prochazka, “The Role of Boron and Carbon in Sintering of Silicon Carbide,” Special Ceramics, Vol. 6, edited by P. Popper, Stoke-On-Trent, England, 1975, pp. 171-181), Carbon (C), Beryllium (Be), (U.S. Pat. No. 4,172,109), and Aluminum (Al), (D. H. Stutz, S. Prochazka, J. Lorenz, “Sintering and Microstructure Formation of Beta-SiC,” J. Am. Ceram. Soc., 68, 479-82, (1985). These additives were added for the purpose of promoting solid-state diffusion. Carbon was added for the purpose of cleaning off the SiO2 layer from the silicon carbide surfaces and allowing the surfaces to be activated by B, Be and Al.
In the 1980s and 1990s, work was done on liquid phase sintering of SiC using rare earth oxide additives. This was disclosed in U.S. Pat. Nos. 4,564,490 and 4,569,921 and in an article by L. Cordrey, et al. titled “Sintering of Silicon Carbide with Rare-Earth Oxide Additions,” in Sintering of Advanced Ceramics, v. 7, (1990), pg. 618, edited by C. A. Handwerker, et al. For these materials, the diffusion occurs through the liquid phase instead of through the solid phase. For successful liquid phase sintering, Negita stated that free energy of formation for the metal oxide additives must be more negative than free energy of oxidation for silicon carbide at sintering temperatures. See K. Negita, “Effective Sintering Aids for Silicon Carbide Ceramics: Reactivities of Silicon Carbide with Various Additives,” J. Am. Ceram. Soc., 69, C-308¥C-310, (1986). By using oxide additives that meet this criterion, the oxide additives remain stable and do not result in oxidation and decomposition of the silicon carbide. Oxidation and decomposition of the silicon carbide, besides resulting in lost material, produces gas species that can inhibit sintering. Shown below are the reactions for silicon carbide decomposition along with the temperature in which they have the lowest free energy. It is seen that reaction products change with temperature.
SiC+O2→SiO2(s,l)+C (300¥1800° C.) 1)
⅔SiC+O2→⅔SiO2(s,l)+⅔CO (1800¥2075° C.) 2)
SiC+O2→SiO(g)+CO (2075¥2100° C.) 3)
2 SiC+O2→2Si(s,l)+2CO (2100¥2600° C.) 4)
The free energy versus temperature is shown in
In early 1990s, Andre Ezis at BAE Systems Advanced Ceramics showed that the choice of sintering additive was important in determining ballistic performance. See U.S. Pat. No. 5,354,536. The use of AlN as a sintering additive was shown to result in clean grain boundaries even in grades of SiC with metal impurities and the optimum amount of sintering additive was found to be a function of the surface area. The fracture of these materials was intergranular. The superior ballistic performance of these materials suggests the importance of fracture mechanism and microstructure in determining ballistic behavior. It should be noted that the ballistic event involves significant pulverization of the ceramic. The pulverization characteristics of ceramics, in which a significant mass of material is comminuted into fine particles underneath the projectile, have not been related to static mechanical properties. Static mechanical properties when applied to ballistic properties have generally been applied to cracks forming near the surface of the ceramic during impact.
In SiC for static applications, second phase additions have been added to improve toughness. Specifically, M. Janney, “Mechanical Properties and Oxidation Behavior of a Hot-Pressed SiC-15 vol %-TiB2 Composite,” Ceramic Bulletin, Vol. 66, 322-324, (1987), determined an increase in toughness from 3.1 to 4.3 MPa m ½ with 15 volume percent TiB2 additive (20 weight percent) and G. C. Wei and P. Becher, “Improvement in Mechanical Properties in SiC by Addition of TiC Particles,” Journal American Ceramic Society, 67 571-74 (1984), determined an increase in fracture toughness for different volume percent TiC additive. These carbides and borides are stable versus SiC at high temperatures and have been shown to toughen the material by crack deflection.
In further work, V. D. Krstic and M. Vlajic, U.S. Pat. No. 5,470,806, patented a powder bed technology to liquid phase sinter SiC with transition metal oxide additives for the purpose of fusing the oxides and converting them into carbides during the course of sintering. The powder bed surrounding the part contained silicon carbide, aluminum oxide and carbon and facilitated the conversion to carbides in the sintered body and prevented excessive weight loss during sintering. The part and the powder bed were contained in a sealed graphite crucible. Aluminum oxide was used as the sintering additive to promote rapid densification and minimize reaction times. For an SiC composition containing 6.5 wt. % Al2O3, 2.5 wt. % TiO2, 6.0 wt. % ZrO2 and 2.0 wt. % C, a fracture toughness of 6.3 Mpa m ½ could be achieved while for an SiC composition containing 8.7 wt. % Al2O3, 20.0 wt. % TiO2, 6.3 wt. % ZrO2 and 5.0 wt. % C, a fracture toughness of 7.2 MPa m ½ could be achieved. In these materials, the TiO2 and ZrO2 reacted to TiC and ZrC during sintering. Typical sintered SiC has a fracture toughness of 4.0 to 5.0 MPa m ½.
In an effort to increase the ballistic performance of SiC, Applicants have looked at oxide additives that do not meet Negita's criterion for use as sintering aid and result in carbide formation below or at sintering temperatures. Oxide additives that do not meet Negita's criterion cause the decomposition of SiC by either simultaneous formation of metal carbide, silicon and CO or simultaneous formation of silicon, metal and CO. The generalized equations are shown below.
2SiC(s) +aMvOw (s,l)
SiC(s) +cMvOw (s,l)
In the present invention, ZrO2 additions are added which will result in decomposition of the SiC and formation of ZrC, and some combination of Si, SiO and CO. The present invention demonstrates that ZrO2 can be used to increase ballistic performance of silicon carbide when added in small amounts and using a furnace design in which the atmosphere can be controlled. Both ZrO2 and stabilized ZrO2 such as 3 mole percent Y2O3 stabilized ZrO2 (3TZY) can be used.
Along with decomposition of SiC and ZrO2 during sintering of SiC, volatization reactions involving the SiO2 (native silica on the SiC grain) and ZrO2 to SiO, ZrO, and O2 would be expected in SiC ceramics. The vapor pressure of these species depends on temperature, the amount of SiO2, ZrO2, free carbon, other phases and kinetic considerations. The presence of these species however would not affect the direction of the high temperature decomposition reactions at sintering temperatures of SiC in inert gas or vacuum furnaces.
The present invention relates to compositions for improved ceramic armor. The present invention includes the following objects, aspects and features:
As such, it is a first object of the present invention to provide compositions for improved ceramic armor.
It is a further object of the present invention to provide such a ballistic material in which a powder made up of a zirconium compound is intermixed with a compound including silicon carbide in a desired proportion.
It is a still further object of the present invention to provide such a ballistic material that has controlled defects in its microstructure that enhance resistance to projectile penetration.
These and other objects, aspects and features of the present invention will be better understood from the following detailed description of the preferred embodiments when read in conjunction with the appended drawing figures.
To improve the performance of Silicon Carbide for ballistic applications, Applicants produced composites from starting composition SiC+sintering additive+ZrO2 that reacts to SiC+ZrC. ZrO2 is one of several metal or transition metal oxides that form stable carbides when reacted with SiC at high temperatures. ZrC has moderate strength, high hardness, and high toughness. ZrC, though not used as a ballistic material, because of high density and cost, shares some of the characteristics of an armor material in showing good strength with high hardness. In limited studies, ZrO2/ZrC has been added to SiC in amounts of greater than 5 wt. % for the purposes of toughening. It should be noted that the reaction of ZrO2 to ZrC reduces the molecular weight of the zirconium containing compound from 123.2 g to 103.2 g and the molar volume from 22 cc to 15.3 cc. As such, this reaction has the effect of reducing the weight and volume percent of zirconium containing compound.
In this work, it has been found that small additions, less than 1 wt. % of ZrO2 to the starting powder can, in fact, be beneficial for use in silicon carbide dwell armor. In dwell armor, the ceramic is put into compression and remains intact as a long rod tungsten projectile strikes the surface of the ceramic at velocities up to or exceeding 1500 msec. See P. Lundberg, R. Renstrom, L. Holmberg, “Impact of metallic projectiles on ceramic targets: transition between interface defeat and penetration,” Int. J. Impact Engng., 24, 259-75, (2000). After the period of dwell in which the projectile is ablated, it has been shown that the ceramic cracks and then becomes comminuted. See D. A. Shockey, A. H. Marchand, S. R. Skaggs, G. E. Cort, M. W. Burkett and R. Parker, “Failure Phenomology of Confined Ceramic Targets and Impacting Rods,” Ceramic Armor Materials by Design, edited by J. W. McCauley et al., (The American Ceramic Society, Westerville, Ohio 2002), pp. 385-402. The nature of this comminuted zone is not well understood but ballistic tests have suggested that the fracture behavior of the grains and grain boundaries are of utmost importance. With this in mind, Applicants have introduced small additions of ZrO2 to influence the fracture behavior of the grains and grain boundaries. It was found by Applicants that ZrO2 additions, though not thermodynamically stable as shown in
The regions outside the hatched area will react with SiC and decompose it. The y-axis of the plot correspond to the standard free energy of formation for the reaction
The x-axis of the plot correspond to the standard free energy of formation for the reaction
dMxCy (s,l)+O2(g) →aMvOw (s,l) +fCO(g)
The horizontal and vertical lines correspond to reaction
The thermal expansion of carbides associated with these metals is similar to that of ZrC. The thermal expansions of carbides for Mo, V, Nb, and Ti are between 7 and 8.5×10−6 in/in ° C. while Cr3C2 has a thermal expansion of 11.5×10−6 in/in ° C. As noted, silicon carbide has a thermal expansion of 4.5×10−6 in/in ° C. and the effect of these differences in thermal expansion between SiC and carbides formed from oxides such as zirconia is residual stresses and/or microcracking that preferentially cause intergranular fracture during a ballistic event. Intergranular fracture has been shown by Ezis to be an important feature for ballistic grade SiC and it is significant that these additions do not affect the grain boundary chemistry in ballistic grade SiC and change the mode of fracture. Instead, the formed carbides appear to act as a supplement that effects crack propagation through the mass of SiC grains during comminution. It should be noted that the improvement in ballistic performance from zirconium carbide particles can not be related to a simple improvement in fracture toughness from 2nd phase particles since 2nd phase particles generally only have a toughening effect when used in excess of 5 volume percent. It should also be noted that a partial reaction of the oxide to carbide has minimal effect on residual stresses of these materials due to the oxides high thermal expansion. ZrO2 has a thermal expansion of 12×10−6 in/in ° C. while TiO2 has a thermal expansion between 7 and 10×10−6 in/in ° C. The other oxides associated with the metal have, similarly, a higher thermal expansion than SiC.
In a first example, ZrO2 was added to BAE Systems SiC—N powder by use of Yttria Stabilized Zirconia Grinding Media (TZ-3Y) during ball milling in polypropylene jar. By measuring the attrition of the grinding media, the amount added was found to be 0.72 weight % zirconia. This zirconia, because it is from the wear of milling media, is fine grained in size and well dispersed through the powder. After milling the powder and sintering additive, the powder was dried and sieved as typical powder by BAE Systems Advanced Ceramics PAD SiC—N processing. The material was then hot pressed using typical BAE Systems Advanced Ceramics PAD SiC—N cycle. The material after hot pressing was machined and tested. The density of the hot pressed parts was 3.235 g/cc, which is greater than PAD SiC—N, which has a theoretical density of 3.22 g/cc. The increase in density is due to the addition of zirconia and/or zirconium compounds. As seen in
The produced material with 0.72% zirconia starting additive was shown by Army Research Laboratories to have better ballistic performance than BAE Systems Advanced Ceramics PAD SiC—N for both seam shots and center shots. At a thickness of 0.75″, tiles made with zirconia additions could not be penetrated by threat typically used to penetrate PAD SiC—N. This is despite the projectile being tested at a higher velocity (maximum velocity). Tiles made at 0.5″ thick had an improved v50 compared to PAD SiC—N.
In a second example, ZrO2 was added to BAE Systems Advanced Ceramics PAD SiC SC-1R powder by using Yttria Stabilized Zirconia Grinding Media (TZ-3Y) during ball milling. By measuring the attrition of the grinding media, the amount added was found to be 0.75 weight % zirconia. This zirconia, because it is from the wear of milling media, is on average 0.2 to 2 microns in size and well dispersed through the powder. After milling the powder and sintering additive, the powder was dried and sieved as typical powder by BAE Systems Advanced Ceramics PAD SiC SC-1R processing. The material was then hot pressed using typical BAE Systems Advanced Ceramics PAD SiC SC-1R cycle. The material after hot pressing was machined and tested. The density of the hot pressed parts was 3.235 g/cc, which is greater than PAD SC-1R, which has a theoretical density of 3.22 g/cc. The increase in density is due to the addition of zirconia that reacts to zirconium carbide. PAD SiC SC-1R has an average grain size of 1.5 microns.
The produced material with 0.75% zirconia was shown by Army Research Laboratories to have better ballistic performance than BAE Systems Advanced Ceramics PAD SiC—N and BAE Systems Advanced Ceramics PAD SC-1R. At a thickness of 0.75″, tiles made with zirconia could not be penetrated by a threat typically used to penetrate BAE Systems Advanced Ceramics PAD SiC—N. This was the case despite the projectile being tested at a higher velocity (maximum velocity).
In a third example ZrO2 was added to BAE Systems Advanced Ceramics SiC—N powder by use of Yttria Stabilized Zirconia Grinding Media (TZ-3Y) during ball milling in polypropylene jar. By measuring the attrition of the grinding media, the amount added was found to be 0.3 weight % zirconia. This zirconia, because it is from the wear of milling media, is fine grained in size and well dispersed through the powder. After milling the powder and sintering additive, the powder was dried and sieved as typical powder by BAE Systems Advanced Ceramics PAD SiC—N processing. The material was then hot pressed using typical BAE Systems Advanced Ceramics PAD SiC—N cycle. The material after hot pressing was machined and tested. EDS/SEM analysis indicated that the zirconium carbide had been formed.
The produced material with 0.3% zirconia starting material was shown by Army Research Laboratories to have better ballistic performance than BAE Systems Advanced Ceramics PAD SiC—N in terms of v50. The tests were performed on 0.500″ tiles.
In a fourth example, 8.53 weight percent TZO powder (tetragonal ZrO2 powder with no yttria addition) from Tosoh was added to PAD SiC—N powders by ball milling. These powders have a typical surface area of 14 m2/g and are sub-micron in size. The milling media was typical of what is used for PAD SiC—N. The materials were milled for slightly shorter times and using a different volatile organic solvent to maximize dispersion of the powders. The material was dried and sieved as typical PAD SiC—N powder. The powders were then hot pressed using a modified hot pressing procedure. Compared to conventional PAD SiC—N, the material was found to hot press at a lower temperature, suggesting that the zirconia reacted with the sintering aids/oxides in the system. Despite this interaction with sintering aids/oxides in the system, the zirconia was found to react to zirconium carbide by SEM/EDS analyses suggesting that zirconium carbide is the thermodynamically stable phase at these temperatures. At this concentration of zirconia addition, some zoning in the hot press body was found. Areas of increased zirconium concentration were found. Despite these microstructural inhomogeneities, ballistic performance was found to increase for DOP tests (20% improvement in performance) compared to PAD SiC—B.
In a fifth example, 8.53 weight percent TZ-3Y powder (yttria stabilized ZrO2) from Tosoh was added to the PAD SiC—N powders by ball milling. These powders have an average surface area of 16 m2/g and are sub-micron in size. The milling media was typical of what is used for PAD SiC—N. The material was dried and sieved as typical PAD SiC—N powder and was hot pressed using the same pressure and temperature schedule as used for the material made from 8.53 weight percent TZ-0. This hot pressed material had similar density, microstructural features, and ballistic performance as the material made from 8.53 weight percent TZ-0 material. This suggests the effect of yttria in the TZ-3Y powders is minimal. Both materials made from TZ-0 and TZ-3Y powders had a density of between 3.32 and 3.34 g/cc. This corresponds to at least 99% of theoretical density. The zirconium containing particles in these materials were visible using the backscatter mode of the SEM, see
EDS analysis of Zirconium Rich Particle in FIG. 5
The results from these examples show that the benefit of adding zirconia to the starting material applies over a wide range of weight percent additives and for different size additions. Additions of 11 weight percent zirconia resulted in cracking of the ceramic after densification. The densified material had a density of between 3.38 and 3.40 g/cc, which corresponds to 9 to 10 weight percent reached ZrC or 11 weight percent unreacted ZrO2. This is the upper weight percent addition that is beneficial to ballistic performance of the material. The benefit of zirconia additions at even low concentrations of 0.30%, show that even small additions of 0.1% ZrO2/ZrC, are beneficial to ballistic performance.
The present invention contemplates a densified mixture of a silicon carbide ceramic material and a zirconium compound, the mixture consisting of 0.1 to about 11%, by weight, of zirconium compound before densification as recited in original independent Claim 1. The present invention also contemplates sintering the silicon carbide ceramic material with aluminum nitride as the sintering aid, as recited in original Claim 3 which was dependent upon original independent Claim 1.
As such, an invention has been disclosed in terms of preferred embodiments thereof which fulfill each and every one of the objects of the invention as set forth hereinabove, and provide new and useful compositions for improved ceramic armor of great novelty and utility.
Of course, various changes, modifications and alterations in the teachings of the present invention may be contemplated by those skilled in the art without departing from the intended spirit and scope.
As such, it is intended that the present invention only be limited by the terms of the appended claims.
|U.S. Classification||501/91, 501/88|
|International Classification||C04B35/565, C04B35/56|
|Cooperative Classification||C04B2235/3865, C04B2235/80, C04B2235/3834, C04B2235/786, C04B2235/3839, C04B2235/3244, C04B2235/3246, C04B35/575, C04B2235/77, C04B2235/3225, C04B2235/383|
|May 9, 2006||AS||Assignment|
Owner name: BAE SYSTEMS ADVANCED CERAMICS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ASHKIN, DANIEL;PALICKA, RICHARD;REEL/FRAME:017852/0331
Effective date: 20060505
|Jun 21, 2011||CC||Certificate of correction|
|Feb 21, 2014||FPAY||Fee payment|
Year of fee payment: 4