US20020038582A1 - Composites of powdered fillers and polymer matrix - Google Patents
Composites of powdered fillers and polymer matrix Download PDFInfo
- Publication number
- US20020038582A1 US20020038582A1 US09/345,813 US34581399A US2002038582A1 US 20020038582 A1 US20020038582 A1 US 20020038582A1 US 34581399 A US34581399 A US 34581399A US 2002038582 A1 US2002038582 A1 US 2002038582A1
- Authority
- US
- United States
- Prior art keywords
- particles
- materials
- polymer
- composite mixture
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 75
- 239000000945 filler Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 239000011159 matrix material Substances 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 118
- 239000002245 particle Substances 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 50
- 239000002861 polymer material Substances 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 23
- -1 poly(arylene ether Chemical compound 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 239000002612 dispersion medium Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 235000011837 pasties Nutrition 0.000 claims abstract 3
- 238000004519 manufacturing process Methods 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 10
- 229920000412 polyarylene Polymers 0.000 claims description 9
- 229910010272 inorganic material Inorganic materials 0.000 claims description 8
- 239000011147 inorganic material Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- 239000012254 powdered material Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000000696 magnetic material Substances 0.000 claims description 3
- 239000006249 magnetic particle Substances 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000009969 flowable effect Effects 0.000 claims 3
- 229920006113 non-polar polymer Polymers 0.000 claims 2
- 239000000654 additive Substances 0.000 abstract description 14
- 230000001965 increasing effect Effects 0.000 abstract description 6
- 238000003825 pressing Methods 0.000 abstract description 3
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000004020 conductor Substances 0.000 description 10
- 239000003989 dielectric material Substances 0.000 description 9
- 238000004377 microelectronic Methods 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- BKQXUNGELBDWLS-UHFFFAOYSA-N 9,9-diphenylfluorene Chemical compound C1=CC=CC=C1C1(C=2C=CC=CC=2)C2=CC=CC=C2C2=CC=CC=C21 BKQXUNGELBDWLS-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000001427 coherent effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000005350 fused silica glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- OIAQMFOKAXHPNH-UHFFFAOYSA-N 1,2-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 OIAQMFOKAXHPNH-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910017083 AlN Inorganic materials 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- 101100518697 Arabidopsis thaliana PAE4 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- IGDGIZKERQBUNG-UHFFFAOYSA-N [Cu].[Ba] Chemical compound [Cu].[Ba] IGDGIZKERQBUNG-UHFFFAOYSA-N 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MYXYKQJHZKYWNS-UHFFFAOYSA-N barium neodymium Chemical compound [Ba][Nd] MYXYKQJHZKYWNS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000004883 computer application Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- SSWAPIFTNSBXIS-UHFFFAOYSA-N dioxido(dioxo)tungsten;iron(2+) Chemical compound [Fe+2].[O-][W]([O-])(=O)=O SSWAPIFTNSBXIS-UHFFFAOYSA-N 0.000 description 1
- OJLGWNFZMTVNCX-UHFFFAOYSA-N dioxido(dioxo)tungsten;zirconium(4+) Chemical compound [Zr+4].[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O OJLGWNFZMTVNCX-UHFFFAOYSA-N 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical group 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000005502 phase rule Effects 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium(III) oxide Inorganic materials O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229910014031 strontium zirconium oxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/227—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by organic binder assisted extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B13/00—Conditioning or physical treatment of the material to be shaped
- B29B13/10—Conditioning or physical treatment of the material to be shaped by grinding, e.g. by triturating; by sieving; by filtering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/401—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft having a casing closely surrounding the rotor, e.g. with a plunger for feeding the material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
- B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7466—Combinations of similar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/748—Plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7485—Systems, i.e. flow charts or diagrams; Plants with consecutive mixers, e.g. with premixing some of the components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/38—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in the same barrel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
- B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
- B29C67/242—Moulding mineral aggregates bonded with resin, e.g. resin concrete
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3737—Organic materials with or without a thermoconductive filler
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8361—Mixing plants; Combinations of mixers combining mixing with other treatments with disintegrating
- B01F33/83613—Mixing plants; Combinations of mixers combining mixing with other treatments with disintegrating by grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
- B01J2219/00094—Jackets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/20—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by extruding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
- B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2503/00—Use of resin-bonded materials as filler
- B29K2503/04—Inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/48—Manufacture or treatment of parts, e.g. containers, prior to assembly of the devices, using processes not provided for in a single one of the subgroups H01L21/06 - H01L21/326
- H01L21/4814—Conductive parts
- H01L21/4871—Bases, plates or heatsinks
- H01L21/4882—Assembly of heatsink parts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0212—Resin particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0215—Metallic fillers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0227—Insulating particles having an insulating coating
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0254—Microballoons or hollow filler particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/06—Thermal details
- H05K2201/068—Thermal details wherein the coefficient of thermal expansion is important
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/07—Electric details
- H05K2201/0776—Resistance and impedance
- H05K2201/0792—Means against parasitic impedance; Means against eddy currents
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/08—Magnetic details
- H05K2201/083—Magnetic materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/02—Details related to mechanical or acoustic processing, e.g. drilling, punching, cutting, using ultrasound
- H05K2203/0278—Flat pressure, e.g. for connecting terminals with anisotropic conductive adhesive
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/06—Lamination
- H05K2203/068—Features of the lamination press or of the lamination process, e.g. using special separator sheets
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1194—Thermal treatment leading to a different chemical state of a material, e.g. annealing for stress-relief, aging
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/14—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12014—All metal or with adjacent metals having metal particles
- Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
Definitions
- the invention is concerned with methods for the manufacture of composite materials consisting of particles of finely powdered filler material bonded in a matrix of polymer material, and new composite materials made by such methods.
- the electronics industry is an example of one which makes substantial use of printed wiring boards and substrates as supports and dielectric participants for electronic circuits, such substrates consisting of thin flat pieces produced to exacting specifications as to starting material and physical and electrical properties.
- the history of the industry shows the use of progressively higher operating frequencies and currently for frequencies up to about 800 megahertz (MHz) copper coated circuit boards of glass fiber reinforced polymers, such as epoxies, cyanide esters, polytetrafluoroethylene (PTFE) and polyimides, have been and are still used.
- FR-4 consisting of epoxy resin deposited on a woven glass fabric, because of its ease of manufacture and low cost.
- this material typically has a dielectric constant of 4.3-4.6 and a dissipation factor of 0.016-0.022 and is frequently used in computer related applications below about 500 MHz frequencies.
- Mobile telephones now operate at frequencies of 1-40 GHz and some computers already at 0.5 GHz, with the prospect of higher frequencies in the future.
- the lowest possible value of dielectric constant is preferred in computer applications to improve signal speed.
- FR-4 and similar materials are materials, despite their low cost, are no longer entirely suitable, primarily because of unacceptable dielectric losses, heating up, lack of sufficient uniformity, unacceptable anisotropy, unacceptable mismatch of thermal expansion between the dielectric material and its metallization, and anisotropic thermal expansion problems as the operating temperatures of the substrates fluctuate.
- the dielectric material of the substrates become an active capacitative participant in signal propagation and here the current materials of choice are certain ceramics formed by sintering or firing suitable powdered inorganic materials, such as fused silica; alumina; aluminum nitride; boron nitride; barium titanate; barium titanate complexes such as Ba(Mg 1/3 Ti 2/3 )O 2 , Ba(Zr,Sn)TiO 4 , and BaTiO 3 doped with Sc 2 O 3 and rare earth oxides; alkoxide-derived SrZrO 3 and SrTiO 3 ; and pyrochlore structured Ba(Zr,Nb) oxides.
- Substrates have also been employed consisting of metal powders, and semiconductor powders embedded in a glass or polymer matrix, a
- ceramic substrates that have been used for hybrid electronic circuit applications comprise square plates of 5 cm (2 ins) side, their production usually involving the preparation of a “slip” (slurry) of the finely powdered materials dispersed in a liquid vehicle, dewatering the slip to a stiff leathery mixture, making a “green” preform from the mixture, and then sintering the preform to become the final substrate plate.
- the substrates are required to have highly uniform values of thickness, grain size, grain structure, density, surface flatness and surface finish, with the purpose of obtaining uniform dielectric, thermal and chemical properties, and also to permit the uniform application to the surfaces of fine lines of conductive or resistive metals or inks.
- Such sintered products inherently contain a number of special and very characteristic types of flaws.
- a first consists of fine holes created by the entrainment of bubbles in the ceramic pre-casting slip of sizes in the range about 1-20 micrometers; these bubbles cannot be removed from the slip by known methods and cause residual porosity in the body.
- sintered alumina substrates may have as many as 800 residual bubble holes per sq/cm of surface (5,000 per sq/in).
- Another flaw is triple-point holes at the junctions of the ceramic granules when the substrate has been formed by roll-compacting of spray-dried powder; they are of similar size to the bubble holes and appear in similar numbers per sq/cm.
- the conductive loss at of the interface between conductor and substrate is 1.65 times higher at a RMS roughness of 40 compared to a RMS roughness of 5 (See P.42 of Materials and Processes for Microwave Hybrids, Richard Brown, published 1989 by the International Society for Hybrid Microelectronics of Reston, Va.)
- Dielectric materials are commonly used as insulating layers between circuits, and layers of circuits in multilayer integrated circuits, the most commonly used of which is silica, which in its various modifications has dielectric constants of the order of 3.0-5.0, more usually 4.0-4.5.
- Low values of dielectric constant are preferred and organic polymers inherently usually have low dielectric values in the range 1.9-3.5, so that considerable research and work has been done to try to develop polymers suitable for this special purpose, among which are polyimides (frequently fluorinated), PTFE, and fluorinated poly(arylene ethers), some of the materials having dielectric constants as low as that of air, i.e. 1.00.
- fluorination is the most common modification of the polymers employed in view of the improvements obtained comprising lowered dielectric constants, enhanced optical transparency, and reduced hydrophilicity and solubility in organic solvents, but the fluorination usually results in the polymers exhibiting a degree of polarization which can cause problems in obtaining the desired dielectric properties.
- U.S. Pat. No. 5,658,994 discloses and claims in its broadest aspect an article of manufacture comprising a combination of a dielectric material and a microelectronic device, wherein the dielectric material is provided on the microelectronic device and contains a poly(arylene ether) polymer consisting essentially of non-functional repeating units of the structure:
- Ar 1 ,Ar 2 ,Ar 3 and Ar 4 are individually divalent arylene radicals selected from the group consisting of: phenylene; biphenyl diradical; para-terphenyl diradical; meta-terphenyl diradical; ortho-terphenyl diradical; naphthalene diradical; anthracene diradical; phenanthrene diradical; diradicals of 9,9-diphenylfluorene of specific type; and 4,4′-diradical of dibenzofuran and mixtures thereof, but Ar 1 , Ar 2 , Ar 3 , and Ar 4 , other than the diradical 9,9-diphenylfluorene, are not isomeric equivalents.
- Ar X is a special radical 9,9-bis(4-oxyphenyl)fluorene and Ar 1 and Ar 3 are individually divalent radicals also selected from the group defined in the immediately preceding paragraph.
- Variations in Ar 1 , Ar 2 , Ar 3 and Ar 4 are stated to allow access to a variety of properties such as reduction or elimination of crystallinity, modulus, tensile strength, high glass transition temperature, etc.
- the polymers are said to be essentially chemically inert, have low polarity, have no additional functional or reactive groups, and to be thermally stable at temperatures of 400°-450° C. in inert atmospheres.
- the polymers may also be cross-linked, either by cross-linking itself, through exposure to temperatures in the range of 350°-450° C., or by providing a cross-linking agent, as well as end capping the polymer with known end capping agents, such as phenylethynyl, benzocyclobutene, ethynyl and nitrile.
- end capping agents such as phenylethynyl, benzocyclobutene, ethynyl and nitrile.
- the specified polymers are non-functional in that they are chemically inert and they do not bear any functional groups that are detrimental to their application in the fabrication of microelectronic devices. They do not have carbonyl moieties such as amide, imide and ketone, which promote adsorption of water. They do not bear halogens such as fluorine, chlorine, bromine and iodine which can react with metal sources in metal deposition processes. They are composed essentially of aromatic carbons, except for the bridging carbon in the 9,9-fluorenylidene group, which has much of the character of aromatic carbons due to its proximity to aromatic structures; for the purposes of the invention the carbon is deemed to be a perphenylated carbon.
- the polymers are proposed for use as coatings, layers, encapsulants, barrier regions or barrier layers or substrates in microelectronic devices. These devices may include, but are not limited to multichip modules, integrated circuits, conductive layers in integrated circuits, conductors in circuit patterns of an integrated circuit, circuit boards as well as similar or analogous electronic structures requiring insulating or dielectric regions or layers. They are also proposed for use as a substrate (dielectric material) in circuit boards or printed wiring boards. Such a circuit board has mounted on its surface patterns for various electrical conductor circuits, and may include various reinforcements, such as woven nonconducting fibers, such as glass cloth. Such circuit boards may be single sided as well as double sided or multilayer.
- additives can be used to impart particular target properties, as is conventionally known in the polymer art, including stabilizers, flame retardants, pigments, plasticizers, surfactants, and the like.
- adhesion promoters can be used to adhere the polymers to the appropriate substrates. Such promoters are typified by hexamethyldisilazane, which can be used to interact with available hydroxyl functionality that may be present on a surface, such as a silica surface.
- the principal object of the invention is to provide new methods for manufacturing composite materials consisting of particles of finely powdered filler material bonded together in a matrix of polymer material, such new composite materials, and articles made from such composite materials.
- composite materials comprising particles of finely powdered filler material uniformly distributed in a matrix of polymer material, the materials comprising:
- the polymer material is of maximum dimension or maximum equivalent spherical dimension of 50 ⁇ m.
- FIG. 1 is the first part of a block flow diagram of the specific method and apparatus for the manufacture of the composite materials and articles of the invention, particularly for the manufacture of flat rectangular copper clad substrates intended for use for electronic circuits;
- FIG. 2 is side elevation of a mixer/solvent evaporation mill shown in outline in FIG. 1;
- FIG. 3 is a cross-section through the mill of FIG. 2, taken on the line A-A therein;
- FIG. 4 is another part of the block flow diagram, continuing from FIG. 1;
- FIG. 5 is a further part of the block flow diagram, continuing from FIG. 4;
- FIGS. 6 and 7 are respective part cross sections to a greatly enlarged scale through a small piece of a typical material of the invention in order to show the grain structure thereof, and showing respectively a layer of metal in position to be applied to a surface, and applied to the surface.
- Composite materials of the invention can be made by mixing together the required portion by weight, or by volume, of particles of the chosen non-polar, nonfunctionalized polymer material of sufficiently small dimension, or equivalent spherical dimension, e.g. in the range 0.1 to 50 micrometers, with the corresponding portion by weight or by volume of the chosen filler material, again of sufficiently small dimension, or equivalent spherical dimension, e.g. in the range 0.1 to 50 micrometers, and subjecting the mixture to a temperature sufficient to melt the polymer material, e.g. in the range 280-400° C. and to a pressure, e.g.
- spherical diameter is meant the diameter of a completely spherical particle having the same volume as the specified particle.
- the polymer material preferably is selected from the group comprising polyarylene ether-2, polyarylene ether-3, and polyarylene ether-4, which materials are described in more detail below, while the filler material is selected from the group comprising particles of inorganic material, particles of electromagnetic material, particles of a core of inorganic material covered with a layer of a metal oxide material, particles of metal material particles of magnetic material, and particles of low dielectric constant high melting point polymer material, all of which particles may be hollow.
- the resultant heated and pressurized composite mixture may be formed into a sheet, film or tape, onto a surface of which a layer of copper may be applied, either by sputtering or by direct bonding of copper foil under heat and pressure in a vacuum, the sheet, film or tape being formed by a thermoplastic extrusion process.
- green bodies can be cut from sheet or tape before the heat and pressure step and these green bodies then converted to heated and pressed bodies by a thermoplastic compression process, again to a surface of which a layer of copper can be applied by sputtering or by direct bonding of copper foil under heat and pressure in a vacuum.
- the resultant bodies may comprise substrates for electronic circuits or enclosures for electronic circuits or devices.
- the polymer is used in the form of a solution thereof (usually of about 10% concentration) in a suitable solvent such as cyclohexanone, and the opportunity is taken of employing this solvent also as a liquid dispersion and suspension vehicle for the filler materials.
- a preliminary mixture is first formed of each of the selected finely powdered filler materials, usually inorganic materials, with the selected polymer solution, although in other processes other vehicles may of course also be used.
- the filler material or mixture of materials may be obtained respectively by precipitation or coprecipitation from solutions of suitable precursors, and however obtained should have the required purity, dielectric constant, loss tangent, and particle size distribution.
- up to four different powdered materials can be fed from a delivery and metering system comprising a plurality of hoppers 10 , 12 , 14 and 16 respectively, while the solution of the polymer in the cyclohexanone is fed from its hopper 18 , and suitable surface active functional additives, if required, such as surfactants, plasticizers and lubricants, are fed from a respective hopper 20 .
- Each powdered material can be fed directly to the respective hopper 10 , 12 , 14 , and 16 , or alternatively obtained from respective precipitation or coprecipitation systems 22 , 24 , or 26 (a system for the contents of the hopper 16 is not shown). If the polymer is employed in the form of a powder then it will be fed from the hopper 18 , while the dispersion vehicle will be fed from a respective hopper, or perhaps from the hopper 20 along with the additives.
- each filler powder from its hopper is continuously precision metered by a respective meter 28 , that of the polymer solution is metered by meter 32 , that of the surface active additives is metered by meter 34 , and those of the combined polymer solution/filler or additive flows are metered by respective meters 36 .
- Each preliminary mixture of polymer solution, powders and additives is delivered into a respective drum type mixer/grinding mill 38 , described in more detail below.
- One of the aspects of the invention that also distinguishes it from prior art processes is that it is preferred to use low cost powders of a relatively wide range of particle sizes in order to obtain optimum packing together of the particles, and resultant minimization of the interposed polymer layers, as contrasted with the highly uniform size, and consequently expensive, powders which were required, particularly for the production of fired ceramic substrates to achieve adequate uniformity of processing.
- the respective powder particles Prior to the formation of each mixture the respective powder particles usually consist of particles of a range of sizes and agglomerates of many finer particles that can vary even more widely in size, and this must be corrected, particularly the reduction of the agglomerates back to their individual particles.
- Each mixer/mill 38 operates to mix the components and produce complete dispersion of the powdered material in the liquid vehicle, and also as a grinding mill to mill the respective powder particles and agglomerates to a required size distribution to a obtain a required degree of uniformity, but with a distribution that will also result in a minimum pore volume when compacted.
- the proportions of the powder, polymer solution and additives from the hoppers are such as to obtain a solids content in the respective preliminary mixture in the range of 40-95% by volume, the quantities of the dispersing vehicle and the functional additives being kept as low as possible, but sufficient for the consistency of the mixture to be kept to that of a relatively wet paste or slurry, to permit its free flow through the relatively narrow processing flow passages of the respective mill 38 , and the subsequent machines.
- a viscosity in the range of about 100-10,000 centipoises will usually be satisfactory.
- deagglomeration and dispersion of each preliminary mixture is carried out simultaneously in its respective mill 38 , using for this purpose a special mill which is the subject of my U.S. Pat. No. 5,279,463, issued Jan., 18, 1994, and U.S. Pat. No. 5,538,191, issued Jul., 23, 1996, the disclosures of which are incorporated herein by this reference.
- These special mills may be of two major types, in a first of which the mill has two circular coaxial plate members with a processing gap formed between them; the axis of rotation can be vertical or horizontal. It is preferred however to use the second type of mill, which consists of an inner cylindrical member rotatable about a horizontal axis inside a stationary hollow outer cylindrical member, the axes of the two cylinders being slightly displaced so that the facing walls are more closely spaced together at one longitudinal location around their periphery to form, parallel to the axes, what is referred to as a processing or micro gap, and are more widely spaced at the diametrically opposed longitudinal location to form, again parallel to the axes, what is referred to as a complementary or macro gap.
- the mixture flows through the processing gap producing so-called “supra-Kolmorgoroff” mixing eddies in the portion of the slurry at and close to the macro gap and so-called “sub-Kolmorgoroff” mixing eddies in the micro or processing gap.
- Ultrasonic transducers may be mounted on the stationary member which apply longitudinal pressure oscillations into the processing gap and reinforce the “sub-Kolmorgoroff” mixing eddies.
- Such apparatus is capable of processing relatively thick slurries of sub-micrometer particles in minutes that otherwise can take several days in conventional high shear mixers and ball or sand mills.
- the separate preliminary mixtures are now mixed together to form a combined mixture having the consistency of a uniform slurry or wet paste by passing them into a mixer/mill 40 , in which the combined mixture is subjected to another grinding, deagglomerating and uniform dispersing operation.
- the mixer/mill 40 is again one of the above-mentioned special mills which are the subject of my U.S. Pat. Nos. 5,279,463 and 5,538,191, being also of the type comprising an inner cylindrical member rotatable inside a stationary hollow outer cylindrical member.
- a single mixer/mill 40 is employed in this embodiment, in some processes it may be preferred to employ a chain of two or more such mills depending upon the amount and rate of grinding, deagglomeration and mixing that is required.
- the milled slurry from the mill 40 passes to a mixer/solvent evaporation mill 42 which again is of the type comprising an inner cylindrical member 44 rotatable inside a stationary hollow outer cylindrical member 46 , the paste being carried on the outer cylindrical surface of the member 44 in the form of a thin film 47 .
- a mixer/solvent evaporation mill 42 which again is of the type comprising an inner cylindrical member 44 rotatable inside a stationary hollow outer cylindrical member 46 , the paste being carried on the outer cylindrical surface of the member 44 in the form of a thin film 47 .
- the paste becoming continuously thicker as it travels in a helical path from the feed entry point 48 of the evaporation mill to its discharge outlet 50 as more and more solvent is withdrawn through solvent discharge outlet 52 , from which it passes to a condenser (not shown) for recovery and reuse.
- the evaporation of the solvent from this mill is facilitated by heat from a row of cartridge heaters 54 in the base of the machine, their output being such as to obtain a temperature in the tape body of about 150° C.
- the paste Near to the discharge outlet of the mill the paste is of sufficient stiffness that it can be extruded into a coherent thin tape 56 of the desired dimension in thickness and width using a conventional paste extruding machine 58 .
- this tape Since this tape still contains small amounts of solvent and the additives, it must be subjected to a further heating process in a tunnel dryer oven, and to this end the tape is deposited on an endless conveyor 60 , which passes it through a drying oven 62 , during which passage the solvent and as much as possible of the additives are removed to leave the strip or tape consisting only of a thoroughly and uniformly dispersed composite mixture of the particles of the filler material or materials and the polymer or polymers.
- a suitable temperature for such an oven is, for example, in the range 150-250° C., the heating being carried out slowly to avoid as far as possible the formation of bubble holes by the exiting dispersion medium and additives or additive breakdown products.
- the tape 56 of dried paste is passed through a cutting station 64 , in which it is severed into individual “green” substrate preforms 66 , usually of rectangular shape and of the size required for the electronic circuit board substrate, if that is the use for which the materials are intended.
- the preforms are deposited manually or automatically into the cavity of a heated compression mold comprising heated upper and lower platens 68 and 70 , the cavity being located in the lower heated platen 70 to facilitate the loading process. Once the preform is loaded the mold cavity is closed by the downward moving heated top platen 68 which protrudes into the cavity to compress the preform to its required dimensions and density.
- the temperature to which the preforms are heated in the mold is sufficient to melt the polymer so that it will flow freely under the pressure applied to completely fill the interstices and coat the filler material particles, while the maximum is that at which the ploymer will begin to degrade unacceptably.
- the minimum pressure to be employed is coupled with the choice of temperature, in that it must be sufficient for the melted polymer to flow as described, the pressure and time for which the mold is closed being sufficient for the material of the preforms to attain maximum compaction and density. During the heat and pressure cycle the melted polymer will flow relatively freely and the temperature and pressure are maintained for a period sufficient to ensure that the polymer can completely fill the relatively small interstices between the solid particles in the form of correspondingly very thin layers.
- the temperature is in the range 280-400° C.
- the pressure is in the range 70 MPa to 1,380 MPa (10,150 to 200,000 psi), although a more commercially likely pressure is about 345 MPa (50,000 psi), while pressures as low as 3.5 MPa (500 psi) may be usable.
- the surfaces of the platens that contact the preforms are mirror-finished or better to assist in obtaining the smooth surfaces that are desired for electronic substrates intended for microwave frequency applications.
- nonfunctionalised poly(arylene ethers) employed is that, since they may be cross-linked by exposure to temperatures in the range of 350°-450° C. in the presence of oxygen, it is possible to take the finished substrate through a cycle in which initially the polymer is melted again and thoroughly diffused throughout the body, the polymer at this stage being relatively fluid, and thereafter the temperature is increased until cross-linking and corresponding densification of the polymer takes place.
- the composite mixture may include as an additive a cross-linking agent and/or an end capping agent, so that the desired densification will take place at lower temperatures.
- this ability to crosslink and/or end cap at elevated temperatures makes the materials particularly useful in microelectronic applications because they can readily be applied as low viscosity materials, e.g. even from solution as described, and then converted to a solvent resistant material of maximum density by the heating.
- the substrates 66 issuing from the press are fed to a multi-stand, heated, flattening roller mill 72 in which they are rolled to an accurately controlled thickness and flattened.
- the surfaces of these rolls are also mirror-finished, or better, again in order to obtain the desired final smooth surfaces.
- the sheet, film or tape from which the preforms have been cut usually has a thickness less than about 60 mil, can be less than about 30 mil, may be less than about 10 mil, may be less than about 4 mil, and can even be less than about 1 mil.
- the surfacing means comprises a hot press in which the cut pieces are pressed between a pair of heated platens, the platen surfaces being mirror-finished or better so that a corresponding finish is imparted to the surfaces of the pieces.
- the mirror-finishing of the substrate surfaces and those of the copper pieces is especially important in ultrahigh-frequency applications since, as described above, the currents tend to flow only in the surface layers of the conductors, and uniformity in characteristics of the etched conductors is facilitated by such smooth surfaces.
- the volume percentage of the filler material can be 60% or more, the minimum value being that at which the interposed layers of polymer are somewhat too thick to have the required mechanical strength for the substrate to have the corresponding amount of mechanical strength.
- the maximum value is set by the amount of the particular polymer required to adequately bind the particular filler material to form a strong coherent body.
- they enable the production of composite materials in which the solids content is easily and economically in the range 60%-97% by volume, preferably 70%-97% by volume.
- the volume fraction of the polymer in the mixtures is only that needed to adhere the filler material particles together while filling the pores left in the inorganic powder after its compression to minimum pore, preferably pore-free, high density.
- the relatively small amounts of polymer present in the composite materials must be extremely well and evenly dispersed among the fine particles, and this is readily achievable with the processes employed virtually independently of the particle size of the filler material.
- FIGS. 6 and 7 are respective photo micrograph cross sections through a material of the invention, respectively before and after the mirror finished piece 76 of copper sheet is attached to the mirror-finished surface of the substrate, the material consisting of closely packed particles 82 of the filler material, of irregular size and shape, coated and bound together by polymer material 84 that no longer exists as discrete particles but as thin intervening films and interstice-filling masses.
- the square section of FIG. 6 measures 5 micrometers each side.
- the adhesiveness of the polymers of the invention are sufficient to ensure adequate bonding without the need for reinforcing fibers or fiber-cloth.
- a particular currently preferred group of the selected poly(arylene ether) polymers in which the repeating unit is biphenyl diradical linked with the 4,4′-diradical of 9,9-diphenylfluorene, are designated PAE-2, while another currently preferred group, in which the repeating unit is para-terphenyl diradical linked with the 4,4′-diradical of 9,9-diphenylfluorene, are designated PAE-3, and third currently preferred group, in which the repeating unit is a combination of the units of PAE-2 and PAE-3, are designated PAE4.
- Polymers of weight average molecular weight below about 30,000 are regarded as less desirable for use with the methods of the invention, since even more than the PAE-2/3/4 materials they are not able to form adequately structurally strong films, sheets or any other substantially three-dimensional body, because of a tendency of these relatively thick structures to shatter into a multitude of smaller fragments. I have discovered however that surprisingly even the lower molecular weight materials remain intact and cohesive as thin film depositions in the low micrometer range thicknesses of about 1-3 micrometers and can therefore be used, although the higher molecular weight materials are to be preferred.
- the composites usually require a minimum of 3% by volume of polymer to be present as long as the optimum particle packing of the filler material has been obtained, the remaining 97% solids content comprising the filler dielectric material, residual surface active and coupling agents, and organic or inorganic reinforcing, strength-providing fibers and whiskers, when these are provided.
- Materials of relatively small particle sizes are preferred, particularly for the filler starting materials, and also for the polymer if a solid polymer or polymers is employed.
- the preferred particle size range for the filler starting materials is from 0.01 to 50 micrometers, while that for the polymer is from 0.1 to 50 micrometers.
- the presence of particles of filler material of a range comprising different sizes is preferred, since this improves the capability of dense packing in a manner that reduces the interstitial volume, and consequently facilitates the production of the very thin highly adhesive layers that are characteristic of the invention, besides reducing the amount of polymer required to fill the interstices and adhere the particles together. It can be shown theoretically that the minimum interstitial volume that can be obtained when packing spheres of uniform size is about 45%. Owing to the wider particle size distribution that can be employed, this volume can be reduced considerably further, down to the specified value of about 3%.
- the methods of this invention are particularly applicable to the production of composite materials in which the finely powdered filler material consists of any one or a mixture of the “advanced” materials that are now used in industry for the production of fired ceramic substrates for electronic circuits, the most common of which are aluminium nitride; barium titanate; barium-neodymium titanate; barium copper tungstate; lead titanate; lead magnesium niobate; lead zinc niobate; lead iron niobate; lead iron tungstate; strontium titanate; zirconium tungstate; the chemical and/or physical equivalents of any of the foregoing; alumina; fused quartz; boron nitride; metal powders; and semiconductors.
- the finely powdered filler material consists of any one or a mixture of the “advanced” materials that are now used in industry for the production of fired ceramic substrates for electronic circuits, the most common of which are aluminium nitride
- compositions comprising powdered ferrites and like inductive materials in a polymer matrix have already been produced, used for example in magnetic passive products such as transformers, inductors and ferrite core devices, but the methods used add the powdered filler material into the polymer matrix and their solids contents have generally been limited to not more than about 50% by volume.
- the invention permits the production of such composite materials of higher solids content, e.g. 80% by volume and above.
- the powdered filler material is a tailored blend of two or more individual materials.
- the requirements for substrate materials, especially for very high frequency applications, are very exacting, requiring consideration of a large number of physical properties including filler material content, bulk density (range), surface finish, grain size (average), water absorption(%), flexural strength, modulus of elasticity, coefficient of linear thermal expansion, thermal conductivity, dielectric strength, dielectric constant, dissipation factor, and volume resistivity.
- the possibility of such blending makes it possible to tailor the properties of the substrates to their specific tasks in a manner which is not possible with a sintered ceramic as in most cases the sintering phase rules would be violated and the resulting fired material would fall apart.
- One of the main reasons for combining filler materials in any given ratio is to obtain a mixture with a tailored dielectric constant, which constant will remain uniform over a temperature range from say ⁇ 50° C. to +200° C., and with a very high Q factor (equivalent to a very low loss tangent) desirably above 500 and if possible as high as 5,000.
Abstract
Description
- The invention is concerned with methods for the manufacture of composite materials consisting of particles of finely powdered filler material bonded in a matrix of polymer material, and new composite materials made by such methods.
- The electronics industry is an example of one which makes substantial use of printed wiring boards and substrates as supports and dielectric participants for electronic circuits, such substrates consisting of thin flat pieces produced to exacting specifications as to starting material and physical and electrical properties. The history of the industry shows the use of progressively higher operating frequencies and currently for frequencies up to about 800 megahertz (MHz) copper coated circuit boards of glass fiber reinforced polymers, such as epoxies, cyanide esters, polytetrafluoroethylene (PTFE) and polyimides, have been and are still used. At present one popular laminate material for such applications is FR-4, consisting of epoxy resin deposited on a woven glass fabric, because of its ease of manufacture and low cost. Typically this material has a dielectric constant of 4.3-4.6 and a dissipation factor of 0.016-0.022 and is frequently used in computer related applications below about 500 MHz frequencies. Mobile telephones now operate at frequencies of 1-40 GHz and some computers already at 0.5 GHz, with the prospect of higher frequencies in the future. The lowest possible value of dielectric constant is preferred in computer applications to improve signal speed. At higher operating frequencies above approximately 0.8 GHz, FR-4 and similar materials are materials, despite their low cost, are no longer entirely suitable, primarily because of unacceptable dielectric losses, heating up, lack of sufficient uniformity, unacceptable anisotropy, unacceptable mismatch of thermal expansion between the dielectric material and its metallization, and anisotropic thermal expansion problems as the operating temperatures of the substrates fluctuate. These thermal expansion problems result from the relatively large coefficients of thermal expansion of the polymers used as substrate material, and the unequal expansion coefficients of reinforcing fibers in their length and thickness dimensions. For frequencies above 800 MHz the dielectric material of the substrates become an active capacitative participant in signal propagation and here the current materials of choice are certain ceramics formed by sintering or firing suitable powdered inorganic materials, such as fused silica; alumina; aluminum nitride; boron nitride; barium titanate; barium titanate complexes such as Ba(Mg1/3Ti2/3)O2, Ba(Zr,Sn)TiO4, and BaTiO3 doped with Sc2O3 and rare earth oxides; alkoxide-derived SrZrO3 and SrTiO3; and pyrochlore structured Ba(Zr,Nb) oxides. Substrates have also been employed consisting of metal powders, and semiconductor powders embedded in a glass or polymer matrix, a particular preferred family of polymers being those based on PTFE.
- For example, ceramic substrates that have been used for hybrid electronic circuit applications comprise square plates of 5 cm (2 ins) side, their production usually involving the preparation of a “slip” (slurry) of the finely powdered materials dispersed in a liquid vehicle, dewatering the slip to a stiff leathery mixture, making a “green” preform from the mixture, and then sintering the preform to become the final substrate plate. The substrates are required to have highly uniform values of thickness, grain size, grain structure, density, surface flatness and surface finish, with the purpose of obtaining uniform dielectric, thermal and chemical properties, and also to permit the uniform application to the surfaces of fine lines of conductive or resistive metals or inks.
- Such sintered products inherently contain a number of special and very characteristic types of flaws. A first consists of fine holes created by the entrainment of bubbles in the ceramic pre-casting slip of sizes in the range about 1-20 micrometers; these bubbles cannot be removed from the slip by known methods and cause residual porosity in the body. As an example, sintered alumina substrates may have as many as 800 residual bubble holes per sq/cm of surface (5,000 per sq/in). Another flaw is triple-point holes at the junctions of the ceramic granules when the substrate has been formed by roll-compacting of spray-dried powder; they are of similar size to the bubble holes and appear in similar numbers per sq/cm. Yet another consists of “knit-lines”, which are webs or networks of seam lines of lower density formed at the contact areas between butting particles during cold pressing. Two other common flaws are caused by inclusions of foreign matter into the material during processing, and the enlarged grains caused by agglomeration of the particles despite their initial fine grinding. The usual inclusions are fine particles due to abrasive wear of the grinding media in the mills. Both inclusions and agglomerates will sinter in a matrix at a different rate from the remainder of the matrix and can result in flaws of much greater magnitude than the original inclusion or agglomerate.
- Costly mirror-finishing by diamond machining and lapping of the ceramic surfaces is required to allow the accurate deposition of sputtered metallization layers from which conductor lines are formed by etching. Mirror-finishes are required because the electrical currents at frequencies above 0.8 GHz move predominantly in the skin of a conductor line while in the lower frequencies they occupy the entire crossection of the conductor line. The thickness of the skin through which currents move at GHz frquencies becomes thinner as frequencies rise and are already as thin as 1 to 2 micrometers in copper at around 2 GHz. Any surface roughness of the conductors on the top and bottom sides will therefor contribute to considerable conductive losses. For example, at a frequency of 4 GHz, the conductive loss at of the interface between conductor and substrate is 1.65 times higher at a RMS roughness of 40 compared to a RMS roughness of 5 (See P.42 of Materials and Processes for Microwave Hybrids, Richard Brown, published 1989 by the International Society for Hybrid Microelectronics of Reston, Va.)
- There is therefore continuing interest in methods for manufacturing composite materials for the production of electronic substrates and for use as electronic packaging materials, with which sintering and the high processing temperatures required together with their attendant difficulties, high cost of diamond machining and lapping, and the associated considerable costs are avoided.
- The low inherent mechanical strength of the currently available matrix forming polymers and their excessive thermal expansion coefficient has made it necessary to embed reinforcing materials, such as woven glass fiber cloth, into the substrate body, to strengthen it and also to contrain its excessive thermal expansion. But such reinforcing materials unfortunately cause unacceptable inhomogenity of the structure. For example, the presence of such reinforcing material makes it difficult to incorporate powdered filler materials uniformly into the body of the substrate. Another difficulty is caused by the generally poor adhesion exhibited by the commercially available matrix polymers toward the usual filler materials, and extensive research and development has been undertaken in the past, and is continuing, in connection with known substrate-forming polymers, such as PTFE, to find coupling agents that will provide adequate adhesion between the polymer and the powder components, and thus satisfactory mechanical strength in the resultant substrates.
- Dielectric materials are commonly used as insulating layers between circuits, and layers of circuits in multilayer integrated circuits, the most commonly used of which is silica, which in its various modifications has dielectric constants of the order of 3.0-5.0, more usually 4.0-4.5. Low values of dielectric constant are preferred and organic polymers inherently usually have low dielectric values in the range 1.9-3.5, so that considerable research and work has been done to try to develop polymers suitable for this special purpose, among which are polyimides (frequently fluorinated), PTFE, and fluorinated poly(arylene ethers), some of the materials having dielectric constants as low as that of air, i.e. 1.00. At the present time fluorination is the most common modification of the polymers employed in view of the improvements obtained comprising lowered dielectric constants, enhanced optical transparency, and reduced hydrophilicity and solubility in organic solvents, but the fluorination usually results in the polymers exhibiting a degree of polarization which can cause problems in obtaining the desired dielectric properties.
- U.S. Pat. No. 5,658,994, issued Aug. 19, 1997, and U.S. Pat. No. 5,874,516, issued Feb. 23, 1999, both to Air Products and Chemicals, Inc. of Allentown, Pa., the disclosures of which are incorporated herein by this reference, disclose and claim a unique utility as a dielectric coating material for micro-electronic devices of a class of poly(arylene ethers) as a replacement for silica-based dielectric materials, wherein the poly(arylene ether) does not have nonaromatic carbons (other than perphenylated carbon), fluorinated substituents or significantly polarizable functional groups. These materials, which are relatively easily synthesized, are found surprisingly to have an excellent combination of desirable properties, namely thermal stability, low dielectric constant values, low moisture absorption and low moisture outgassing.
- U.S. Pat. No. 5,658,994 discloses and claims in its broadest aspect an article of manufacture comprising a combination of a dielectric material and a microelectronic device, wherein the dielectric material is provided on the microelectronic device and contains a poly(arylene ether) polymer consisting essentially of non-functional repeating units of the structure:
- —{—O—Ar1—O—Ar2—}m—{—O—Ar3—O—Ar4—}n—
- wherein m=0 to 1.0; and n=1.0-m; and Ar1,Ar2,Ar3 and Ar4 are individually divalent arylene radicals selected from the group consisting of: phenylene; biphenyl diradical; para-terphenyl diradical; meta-terphenyl diradical; ortho-terphenyl diradical; naphthalene diradical; anthracene diradical; phenanthrene diradical; diradicals of 9,9-diphenylfluorene of specific type; and 4,4′-diradical of dibenzofuran and mixtures thereof, but Ar1, Ar2, Ar3, and Ar4, other than the diradical 9,9-diphenylfluorene, are not isomeric equivalents.
- U.S. Pat. No. 5,874,516 claims poly(arylene ether) consisting essentially of non-functional repeating units of the structure:
- —{—O—Arx—O—Ar1—}m—{—O—Ar2—O—Ar3—}n—
- wherein m=0.2 to 1.0; and n=1.0-m; and Ar1, Ar2,and Ar3 are individually divalent radicals selected from the group defined in the preceding paragraph; or essentially of non-functional repeating units of the structure:
- —{—O—ArX—O—Ar1—}m—{—O—ArX—O—Ar3—}n—
- wherein m=0 to 1.0; and n=1.0-m; ArX is a special radical 9,9-bis(4-oxyphenyl)fluorene and Ar1 and Ar3 are individually divalent radicals also selected from the group defined in the immediately preceding paragraph.
- Variations in Ar1, Ar2, Ar3 and Ar4 are stated to allow access to a variety of properties such as reduction or elimination of crystallinity, modulus, tensile strength, high glass transition temperature, etc. The polymers are said to be essentially chemically inert, have low polarity, have no additional functional or reactive groups, and to be thermally stable at temperatures of 400°-450° C. in inert atmospheres. In addition to the basic polymer structures as outlined above the polymers may also be cross-linked, either by cross-linking itself, through exposure to temperatures in the range of 350°-450° C., or by providing a cross-linking agent, as well as end capping the polymer with known end capping agents, such as phenylethynyl, benzocyclobutene, ethynyl and nitrile. The ability to crosslink at elevated temperatures, with the consequent marked increase in molecular weight and density makes the materials particularly useful in microelectronic applications because they can readily be applied from solution and then converted to a solvent resistant coating by heating.
- The specified polymers are non-functional in that they are chemically inert and they do not bear any functional groups that are detrimental to their application in the fabrication of microelectronic devices. They do not have carbonyl moieties such as amide, imide and ketone, which promote adsorption of water. They do not bear halogens such as fluorine, chlorine, bromine and iodine which can react with metal sources in metal deposition processes. They are composed essentially of aromatic carbons, except for the bridging carbon in the 9,9-fluorenylidene group, which has much of the character of aromatic carbons due to its proximity to aromatic structures; for the purposes of the invention the carbon is deemed to be a perphenylated carbon.
- The polymers are proposed for use as coatings, layers, encapsulants, barrier regions or barrier layers or substrates in microelectronic devices. These devices may include, but are not limited to multichip modules, integrated circuits, conductive layers in integrated circuits, conductors in circuit patterns of an integrated circuit, circuit boards as well as similar or analogous electronic structures requiring insulating or dielectric regions or layers. They are also proposed for use as a substrate (dielectric material) in circuit boards or printed wiring boards. Such a circuit board has mounted on its surface patterns for various electrical conductor circuits, and may include various reinforcements, such as woven nonconducting fibers, such as glass cloth. Such circuit boards may be single sided as well as double sided or multilayer.
- It is proposed that additives can be used to impart particular target properties, as is conventionally known in the polymer art, including stabilizers, flame retardants, pigments, plasticizers, surfactants, and the like. It is also proposed that adhesion promoters can be used to adhere the polymers to the appropriate substrates. Such promoters are typified by hexamethyldisilazane, which can be used to interact with available hydroxyl functionality that may be present on a surface, such as a silica surface.
- The principal object of the invention is to provide new methods for manufacturing composite materials consisting of particles of finely powdered filler material bonded together in a matrix of polymer material, such new composite materials, and articles made from such composite materials.
- It is another object to provide such new methods with which the resultant composite materials and articles comprises at least 60 percent by volume of the filler material, with the remainder consisting of the polymer material matrix together with any necessary additives.
- In accordance with the invention there is provided a method of manufacturing composite materials comprising particles of finely powdered filler material uniformly distributed in a matrix of polymer material, the method comprising the steps of:
- mixing together from 60 to 97 volume percent of particles of the filler material of minimum pore volume when compacted and the balance of polymer bonding material consisting of nonfunctionalized poly(arylene ether) to form a composite mixture; and
- subjecting the composite mixture to a temperature sufficient to melt the polymer material and to a pressure sufficient to uniformly disperse the melted polymer material into the interstices between the particles of filler material.
- Also in accordance with the invention there are provided composite materials comprising particles of finely powdered filler material uniformly distributed in a matrix of polymer material, the materials comprising:
- from 60 to 97 volume percent of particles of the compacted filler material and the balance of polymer material consisting of nonfunctionalized poly(arylene ether) together forming a uniform composite mixture;
- wherein the composite mixture has been subjected to a temperature sufficient to melt the polymer material and to a pressure sufficient to uniformly disperse the melted polymer material into the interstices between the particles of filler material.
- Preferably the polymer material is of maximum dimension or maximum equivalent spherical dimension of 50 μm.
- Methods and apparatus for the production of the new composite materials, and new composite materials and articles made of such new composite materials, produced using such methods and apparatus, that are particular preferred embodiments of the invention will now be described, by way of example, with reference to the accompanying diagrammatic drawings wherein:
- FIG. 1 is the first part of a block flow diagram of the specific method and apparatus for the manufacture of the composite materials and articles of the invention, particularly for the manufacture of flat rectangular copper clad substrates intended for use for electronic circuits;
- FIG. 2 is side elevation of a mixer/solvent evaporation mill shown in outline in FIG. 1;
- FIG. 3 is a cross-section through the mill of FIG. 2, taken on the line A-A therein;
- FIG. 4 is another part of the block flow diagram, continuing from FIG. 1;
- FIG. 5 is a further part of the block flow diagram, continuing from FIG. 4; and
- FIGS. 6 and 7 are respective part cross sections to a greatly enlarged scale through a small piece of a typical material of the invention in order to show the grain structure thereof, and showing respectively a layer of metal in position to be applied to a surface, and applied to the surface.
- I have discovered that unexpectedly a particular sub-family of a known family of polymers, namely poly(arylene ethers), exhibit unusually high inherent adhesiveness toward finely ground filler materials of the kind that can be employed in combination with matrix materials to produce electronic substrates and that, also unexpectedly, the production of useful composite materials requires a complete reversal of approach from that which has previously been employed in the production of composite materials. A major problem in the prior art processes of forming composite materials, and in the substrates obtained thereby, is the progressive loss of mechanical strength that results as the filler solids content is increased, and hitherto attempts to incorporate more than about 40 volume percent generally has resulted in composite which are so friable that they literally collapse to a heap of sand-like material if in testing they are stressed to the degree required in commercial practice. Moreover, it has been found difficult with prior art processes to incorporate as much as 40 volume percent solids material, since the mixtures become so viscous that uniform mixing is virtually impossible. Consequently, the approach has of necessity been to incorporate only as much filler material as will result in a substrate of adequate mechanical strength, and to accept the lower desired electrical characteristics that result. I have discovered however that with the methods of the invention, for the successful production of composite materials, the solids content must instead be increased to values well beyond those of the conventional prior art. An acceptable minimum for my new composite materials is 60 volume percent, in that such materials are of the required minimum mechanical strength, it being found that the mechanical strength increases with increased solids content, instead of decreasing, up to the value of about 95-97 volume percent, or beyond which the proportion of polymer is reduced below the minimum value required to maintain adequate adhesion between the uniformly distributed filler particles. It is my belief that a possible explanation for this highly unexpected result, although other explanations may be possible, and therefore I do not intend that the invention be limited thereby, is that although the chosen polymers exhibit unusually high adhesion, especially toward oxide materials such as silica, aluminum oxide, metal powders and boron nitride, they are not particularly mechanically strong, and therefore are most effective in this new and special application if employed in the form of very thin adherent layers interposed between the filler particles, such can only be obtained with the methods of the invention and when the solids content is sufficiently high. It is difficult to specify with any degree of accuracy the optimum thicknesses for the interposed layers; it is known that layers of 1-3 micrometers are very successful in giving superior adhesion with adequate strength, and a possible upper limit is 40 micrometers (0.001 in).
- Composite materials of the invention can be made by mixing together the required portion by weight, or by volume, of particles of the chosen non-polar, nonfunctionalized polymer material of sufficiently small dimension, or equivalent spherical dimension, e.g. in the range 0.1 to 50 micrometers, with the corresponding portion by weight or by volume of the chosen filler material, again of sufficiently small dimension, or equivalent spherical dimension, e.g. in the range 0.1 to 50 micrometers, and subjecting the mixture to a temperature sufficient to melt the polymer material, e.g. in the range 280-400° C. and to a pressure, e.g. in the range 3.5 to 1,380 MPa (500 to 200,000 psi), preferably 70 to 1,380 MPa (10,000 to 200,00 psi), sufficient to disperse the melted polymer material into the interstices between the particles of filler material. By equivalent spherical diameter is meant the diameter of a completely spherical particle having the same volume as the specified particle. In alternative processes which are described in more detail below the polymer may be added in the form of a solution thereof, provided steps are taken to remove all of the solvent once the filler and polymer materials have been uniformly mixed together. The polymer material preferably is selected from the group comprising polyarylene ether-2, polyarylene ether-3, and polyarylene ether-4, which materials are described in more detail below, while the filler material is selected from the group comprising particles of inorganic material, particles of electromagnetic material, particles of a core of inorganic material covered with a layer of a metal oxide material, particles of metal material particles of magnetic material, and particles of low dielectric constant high melting point polymer material, all of which particles may be hollow.
- The resultant heated and pressurized composite mixture may be formed into a sheet, film or tape, onto a surface of which a layer of copper may be applied, either by sputtering or by direct bonding of copper foil under heat and pressure in a vacuum, the sheet, film or tape being formed by a thermoplastic extrusion process. Alternatively, green bodies can be cut from sheet or tape before the heat and pressure step and these green bodies then converted to heated and pressed bodies by a thermoplastic compression process, again to a surface of which a layer of copper can be applied by sputtering or by direct bonding of copper foil under heat and pressure in a vacuum. The resultant bodies may comprise substrates for electronic circuits or enclosures for electronic circuits or devices. The processes of the invention will be described in detail below in connection with the manufacture of such thin flat plates, but it will be apparent that they are applicable also to any shape of molded article with which direct production of superior surface finish, highly uniform micro-structures, and high dimensional uniformity from finished article to article is desired.
- With microelectronic devices, and with the higher frequencies now employed, the problems of adequate uniformity of physical and chemical constitution and physical and electrical properties of the substrates have been exacerbated, and the simple mixing processes described above usually will not provide sufficient uniformity, and in such case it becomes necessary to employ a method and apparatus as described in detail below.
- Referring now to FIG. 1, in this particular process it is assumed that a mixture of different filler materials are to be used, especially in view of the opportunity this provides of specifically tailoring the mechanical and electrical characteristics of the resultant substrates for the end product. The polymer is used in the form of a solution thereof (usually of about 10% concentration) in a suitable solvent such as cyclohexanone, and the opportunity is taken of employing this solvent also as a liquid dispersion and suspension vehicle for the filler materials. A preliminary mixture is first formed of each of the selected finely powdered filler materials, usually inorganic materials, with the selected polymer solution, although in other processes other vehicles may of course also be used. The filler material or mixture of materials may be obtained respectively by precipitation or coprecipitation from solutions of suitable precursors, and however obtained should have the required purity, dielectric constant, loss tangent, and particle size distribution. In this embodiment up to four different powdered materials can be fed from a delivery and metering system comprising a plurality of
hoppers hopper 18, and suitable surface active functional additives, if required, such as surfactants, plasticizers and lubricants, are fed from arespective hopper 20. Each powdered material can be fed directly to therespective hopper coprecipitation systems hopper 16 is not shown). If the polymer is employed in the form of a powder then it will be fed from thehopper 18, while the dispersion vehicle will be fed from a respective hopper, or perhaps from thehopper 20 along with the additives. The flow of each filler powder from its hopper is continuously precision metered by arespective meter 28, that of the polymer solution is metered bymeter 32, that of the surface active additives is metered bymeter 34, and those of the combined polymer solution/filler or additive flows are metered byrespective meters 36. Each preliminary mixture of polymer solution, powders and additives is delivered into a respective drum type mixer/grindingmill 38, described in more detail below. - One of the aspects of the invention that also distinguishes it from prior art processes is that it is preferred to use low cost powders of a relatively wide range of particle sizes in order to obtain optimum packing together of the particles, and resultant minimization of the interposed polymer layers, as contrasted with the highly uniform size, and consequently expensive, powders which were required, particularly for the production of fired ceramic substrates to achieve adequate uniformity of processing. Prior to the formation of each mixture the respective powder particles usually consist of particles of a range of sizes and agglomerates of many finer particles that can vary even more widely in size, and this must be corrected, particularly the reduction of the agglomerates back to their individual particles. Each mixer/
mill 38 operates to mix the components and produce complete dispersion of the powdered material in the liquid vehicle, and also as a grinding mill to mill the respective powder particles and agglomerates to a required size distribution to a obtain a required degree of uniformity, but with a distribution that will also result in a minimum pore volume when compacted. - The proportions of the powder, polymer solution and additives from the hoppers are such as to obtain a solids content in the respective preliminary mixture in the range of 40-95% by volume, the quantities of the dispersing vehicle and the functional additives being kept as low as possible, but sufficient for the consistency of the mixture to be kept to that of a relatively wet paste or slurry, to permit its free flow through the relatively narrow processing flow passages of the
respective mill 38, and the subsequent machines. A viscosity in the range of about 100-10,000 centipoises will usually be satisfactory. In the methods of the invention preferably such grinding, deagglomeration and dispersion of each preliminary mixture is carried out simultaneously in itsrespective mill 38, using for this purpose a special mill which is the subject of my U.S. Pat. No. 5,279,463, issued Jan., 18, 1994, and U.S. Pat. No. 5,538,191, issued Jul., 23, 1996, the disclosures of which are incorporated herein by this reference. - These special mills may be of two major types, in a first of which the mill has two circular coaxial plate members with a processing gap formed between them; the axis of rotation can be vertical or horizontal. It is preferred however to use the second type of mill, which consists of an inner cylindrical member rotatable about a horizontal axis inside a stationary hollow outer cylindrical member, the axes of the two cylinders being slightly displaced so that the facing walls are more closely spaced together at one longitudinal location around their periphery to form, parallel to the axes, what is referred to as a processing or micro gap, and are more widely spaced at the diametrically opposed longitudinal location to form, again parallel to the axes, what is referred to as a complementary or macro gap. The mixture flows through the processing gap producing so-called “supra-Kolmorgoroff” mixing eddies in the portion of the slurry at and close to the macro gap and so-called “sub-Kolmorgoroff” mixing eddies in the micro or processing gap. Ultrasonic transducers may be mounted on the stationary member which apply longitudinal pressure oscillations into the processing gap and reinforce the “sub-Kolmorgoroff” mixing eddies. Such apparatus is capable of processing relatively thick slurries of sub-micrometer particles in minutes that otherwise can take several days in conventional high shear mixers and ball or sand mills.
- The separate preliminary mixtures are now mixed together to form a combined mixture having the consistency of a uniform slurry or wet paste by passing them into a mixer/
mill 40, in which the combined mixture is subjected to another grinding, deagglomerating and uniform dispersing operation. The mixer/mill 40 is again one of the above-mentioned special mills which are the subject of my U.S. Pat. Nos. 5,279,463 and 5,538,191, being also of the type comprising an inner cylindrical member rotatable inside a stationary hollow outer cylindrical member. Although only a single mixer/mill 40 is employed in this embodiment, in some processes it may be preferred to employ a chain of two or more such mills depending upon the amount and rate of grinding, deagglomeration and mixing that is required. - The milled slurry from the
mill 40 passes to a mixer/solvent evaporation mill 42 which again is of the type comprising an innercylindrical member 44 rotatable inside a stationary hollow outercylindrical member 46, the paste being carried on the outer cylindrical surface of themember 44 in the form of athin film 47. In the mill most of the cyclohexanone solvent is removed while the paste is vigorously mixed, the paste becoming continuously thicker as it travels in a helical path from thefeed entry point 48 of the evaporation mill to itsdischarge outlet 50 as more and more solvent is withdrawn throughsolvent discharge outlet 52, from which it passes to a condenser (not shown) for recovery and reuse. The evaporation of the solvent from this mill is facilitated by heat from a row ofcartridge heaters 54 in the base of the machine, their output being such as to obtain a temperature in the tape body of about 150° C. Near to the discharge outlet of the mill the paste is of sufficient stiffness that it can be extruded into a coherentthin tape 56 of the desired dimension in thickness and width using a conventionalpaste extruding machine 58. Since this tape still contains small amounts of solvent and the additives, it must be subjected to a further heating process in a tunnel dryer oven, and to this end the tape is deposited on anendless conveyor 60, which passes it through a dryingoven 62, during which passage the solvent and as much as possible of the additives are removed to leave the strip or tape consisting only of a thoroughly and uniformly dispersed composite mixture of the particles of the filler material or materials and the polymer or polymers. A suitable temperature for such an oven is, for example, in the range 150-250° C., the heating being carried out slowly to avoid as far as possible the formation of bubble holes by the exiting dispersion medium and additives or additive breakdown products. - The
tape 56 of dried paste is passed through a cuttingstation 64, in which it is severed into individual “green” substrate preforms 66, usually of rectangular shape and of the size required for the electronic circuit board substrate, if that is the use for which the materials are intended. The preforms are deposited manually or automatically into the cavity of a heated compression mold comprising heated upper andlower platens heated platen 70 to facilitate the loading process. Once the preform is loaded the mold cavity is closed by the downward moving heatedtop platen 68 which protrudes into the cavity to compress the preform to its required dimensions and density. The temperature to which the preforms are heated in the mold is sufficient to melt the polymer so that it will flow freely under the pressure applied to completely fill the interstices and coat the filler material particles, while the maximum is that at which the ploymer will begin to degrade unacceptably. The minimum pressure to be employed is coupled with the choice of temperature, in that it must be sufficient for the melted polymer to flow as described, the pressure and time for which the mold is closed being sufficient for the material of the preforms to attain maximum compaction and density. During the heat and pressure cycle the melted polymer will flow relatively freely and the temperature and pressure are maintained for a period sufficient to ensure that the polymer can completely fill the relatively small interstices between the solid particles in the form of correspondingly very thin layers. Typically the temperature is in the range 280-400° C., while the pressure is in therange 70 MPa to 1,380 MPa (10,150 to 200,000 psi), although a more commercially likely pressure is about 345 MPa (50,000 psi), while pressures as low as 3.5 MPa (500 psi) may be usable. The surfaces of the platens that contact the preforms are mirror-finished or better to assist in obtaining the smooth surfaces that are desired for electronic substrates intended for microwave frequency applications. - Another unexpected advantage of the nonfunctionalised poly(arylene ethers) employed is that, since they may be cross-linked by exposure to temperatures in the range of 350°-450° C. in the presence of oxygen, it is possible to take the finished substrate through a cycle in which initially the polymer is melted again and thoroughly diffused throughout the body, the polymer at this stage being relatively fluid, and thereafter the temperature is increased until cross-linking and corresponding densification of the polymer takes place. Alternatively, the composite mixture may include as an additive a cross-linking agent and/or an end capping agent, so that the desired densification will take place at lower temperatures. As described above this ability to crosslink and/or end cap at elevated temperatures makes the materials particularly useful in microelectronic applications because they can readily be applied as low viscosity materials, e.g. even from solution as described, and then converted to a solvent resistant material of maximum density by the heating.
- The
substrates 66 issuing from the press are fed to a multi-stand, heated, flatteningroller mill 72 in which they are rolled to an accurately controlled thickness and flattened. The surfaces of these rolls are also mirror-finished, or better, again in order to obtain the desired final smooth surfaces. The sheet, film or tape from which the preforms have been cut usually has a thickness less than about 60 mil, can be less than about 30 mil, may be less than about 10 mil, may be less than about 4 mil, and can even be less than about 1 mil. Substrates intended for use in electronic circuits will usually be of thickness in the range 0.125 mm to 1.5 mm (5-60 mil), and if intended for thick film usage are usually required to be smooth to about 0.75-0.90 micrometer (22-40 microins), while if intended for thin film usage must be flat to better than 0.05 micrometer (2 microins). The preforms are now fed to aheated laminating press 74 in which they are each laminated on one or both sides with a thin flatsmooth piece 76 of copper sheet of the same size, which subsequently is etched to produce the electric circuit. These sheet copper pieces are obtained by cutting from astrip 78 supplied from a roll thereof (not shown) which is cut into pieces at a cutting and mirror-finish surfacing station 80. The surfacing means comprises a hot press in which the cut pieces are pressed between a pair of heated platens, the platen surfaces being mirror-finished or better so that a corresponding finish is imparted to the surfaces of the pieces. The mirror-finishing of the substrate surfaces and those of the copper pieces is especially important in ultrahigh-frequency applications since, as described above, the currents tend to flow only in the surface layers of the conductors, and uniformity in characteristics of the etched conductors is facilitated by such smooth surfaces. - With the processes of the invention the volume percentage of the filler material can be 60% or more, the minimum value being that at which the interposed layers of polymer are somewhat too thick to have the required mechanical strength for the substrate to have the corresponding amount of mechanical strength. The maximum value is set by the amount of the particular polymer required to adequately bind the particular filler material to form a strong coherent body. Thus, they enable the production of composite materials in which the solids content is easily and economically in the
range 60%-97% by volume, preferably 70%-97% by volume. The volume fraction of the polymer in the mixtures is only that needed to adhere the filler material particles together while filling the pores left in the inorganic powder after its compression to minimum pore, preferably pore-free, high density. The relatively small amounts of polymer present in the composite materials must be extremely well and evenly dispersed among the fine particles, and this is readily achievable with the processes employed virtually independently of the particle size of the filler material. - The process and apparatus described above are particularly suited for high volume production of composite materials, but simpler processes requiring less apparatus are also within the scope of the invention. For example, as described above it is also possible to mix together the finely divided filler material and polymer, the dispersion medium, and its necessary additives and thereafter rely upon its processing in one or a series of mixer/
mills 38 and/or 40 to produce the required thorough dispersion, while at the same time obtaining the preferred range of particle sizes, the dispersed mixture that is produced thereafter being passed to the dryingoven 46 etc., as with the prior process. - In many applications the degree of uniformity required in the material of the finished substrate is such that even the extensive specific process described above may not be sufficient, and it may be necessary to apply an additional series of steps in which the substrates are broken and ground back down to about the original particle size distribution, with the difference that the filler material particles are now intimately associated with particles and thin coatings of the polymer. This finely divided material is again ground and dispersed in a suitable medium by use of one or a chain of the special mills, such as the
mills - FIGS. 6 and 7 are respective photo micrograph cross sections through a material of the invention, respectively before and after the mirror finished
piece 76 of copper sheet is attached to the mirror-finished surface of the substrate, the material consisting of closelypacked particles 82 of the filler material, of irregular size and shape, coated and bound together bypolymer material 84 that no longer exists as discrete particles but as thin intervening films and interstice-filling masses. As an indication of the size of the particles, etc. involved the square section of FIG. 6 measures 5 micrometers each side. The adhesiveness of the polymers of the invention are sufficient to ensure adequate bonding without the need for reinforcing fibers or fiber-cloth. - A particular currently preferred group of the selected poly(arylene ether) polymers, in which the repeating unit is biphenyl diradical linked with the 4,4′-diradical of 9,9-diphenylfluorene, are designated PAE-2, while another currently preferred group, in which the repeating unit is para-terphenyl diradical linked with the 4,4′-diradical of 9,9-diphenylfluorene, are designated PAE-3, and third currently preferred group, in which the repeating unit is a combination of the units of PAE-2 and PAE-3, are designated PAE4. Methods for the production of these polymers are disclosed in the above-mentioned U.S. Pat. Nos 5,658,994 and 5,874,516, to which reference may be made. Samples of these polymers are found to have the following principal characteristics:
PAE-2 PAE-3 PAE-4 Weight average molecular 65,300 45,400 75,800 weight Mw Number average molecular 20,700 11,400 25,700 weight Mn Mw/Mn 2.58 3.98 2.95 Glass transition temperature 257° C. 271° C. 273° C. Tg via DSC Tensile modulus (dynes/cm2) 1.45 × 1010 1.45 × 1010 .39 × 1010 Weight loss % at 400° C. 0.36 0.57 0.65 after 6 hrs Weight loss % at 450° C. 0.91 1.65 1.26 after 6 hrs Wt % gain moisture at 0.279 0.301 0.274 85° F./85RH - In the above-mentioned U.S. patents these materials are described as having improved properties, as compared with prior art fluorinated poly(arylene ether) materials designated PAE-1, a particular sample of which has the following comparable characteristics:
PAE-1 Weight average molecular weight Mw 20,000 Number average molecular weight Mn 7,700 Mw/Mn 2.58 Glass transition temperature Tg via DSC 166° C. Tensile modulus (dynes/cm2) 1.23 × 1010 Weight loss % at 400° C. after 6 hrs 0.72 Weight loss % at 450° C. after 6 hrs 3.16 - Substrates made using PAE-2 have been very successful; the material does not oxidise in air, is highly adhesive without the use of coupling agents, and has a loss tangent in the frequency range of particular interest (1-10 GHz) less than 0.0008, as compared to most other thermoset polymer materials presently used for electronic circuit applications, namely 0.02-0.005. The polymer is thermoplastic and can be processed at 280-300° C., and by post treating the substrates at 300-400° C. to establish cross-linking they can be renedered thermoset, when the loss tangent drops below 0.0008. Polymers of weight average molecular weight below about 30,000 are regarded as less desirable for use with the methods of the invention, since even more than the PAE-2/3/4 materials they are not able to form adequately structurally strong films, sheets or any other substantially three-dimensional body, because of a tendency of these relatively thick structures to shatter into a multitude of smaller fragments. I have discovered however that surprisingly even the lower molecular weight materials remain intact and cohesive as thin film depositions in the low micrometer range thicknesses of about 1-3 micrometers and can therefore be used, although the higher molecular weight materials are to be preferred.
- The relative proportions of the filler materials and of the polymer depend at least to some extent upon the use to which the substrate is to be put; if a very high frequency circuit is to be installed then it will be preferred to have the maximum amount of filler dielectric material and the minimum amount of polymer. As has been described above, the minimum amount of polymer is set by that required to fill the intergrain interstices when the interstitial volume is at its minimum value, and to ensure sufficient coating of the grains for the resulting composite to have the required mechanical strength. For this reason the composites usually require a minimum of 3% by volume of polymer to be present as long as the optimum particle packing of the filler material has been obtained, the remaining 97% solids content comprising the filler dielectric material, residual surface active and coupling agents, and organic or inorganic reinforcing, strength-providing fibers and whiskers, when these are provided.
- Materials of relatively small particle sizes are preferred, particularly for the filler starting materials, and also for the polymer if a solid polymer or polymers is employed. The preferred particle size range for the filler starting materials is from 0.01 to 50 micrometers, while that for the polymer is from 0.1 to 50 micrometers. As described above, the presence of particles of filler material of a range comprising different sizes is preferred, since this improves the capability of dense packing in a manner that reduces the interstitial volume, and consequently facilitates the production of the very thin highly adhesive layers that are characteristic of the invention, besides reducing the amount of polymer required to fill the interstices and adhere the particles together. It can be shown theoretically that the minimum interstitial volume that can be obtained when packing spheres of uniform size is about 45%. Owing to the wider particle size distribution that can be employed, this volume can be reduced considerably further, down to the specified value of about 3%.
- As described above, there are a number of important parameters for the resultant substrates which must be considered in making a selection of the fillers and polymers to be used. Among those which require the highest possible values are tensile strength; peel strength; solder joint reliability; compliance i.e. low modulus; plated through hole reliability; dielectric constant; chemical inertness; dimensional stability and Q factor. Among those which require the lowest possible values are water absorption, crosstalk v line spacing, and loss tangent or dissipation factor (reciprocal of Q factor).
- The methods of this invention are particularly applicable to the production of composite materials in which the finely powdered filler material consists of any one or a mixture of the “advanced” materials that are now used in industry for the production of fired ceramic substrates for electronic circuits, the most common of which are aluminium nitride; barium titanate; barium-neodymium titanate; barium copper tungstate; lead titanate; lead magnesium niobate; lead zinc niobate; lead iron niobate; lead iron tungstate; strontium titanate; zirconium tungstate; the chemical and/or physical equivalents of any of the foregoing; alumina; fused quartz; boron nitride; metal powders; and semiconductors. Another important group is compositions comprising powdered ferrites and like inductive materials in a polymer matrix have already been produced, used for example in magnetic passive products such as transformers, inductors and ferrite core devices, but the methods used add the powdered filler material into the polymer matrix and their solids contents have generally been limited to not more than about 50% by volume. The invention permits the production of such composite materials of higher solids content, e.g. 80% by volume and above.
- At this time the only ceramic materials with temperature stable dielectric constants that are available have values in the ranges 2.6 to 12, 37 to 39 and 80 to 90, whereas in the quickly expanding market of wireless telecommunication, which is based on microwave frequencies ranging from 800 MHz to over 30 GHz, and in which small size and low weight are of increasing importance, the preferred dielectric constant values need to be tailored to be anywhere between 8 and 2000, according to choices dictated by the optimum circuit architecture, instead of, as at present, the circuit architecture being dictated by the very limited ranges of dielectric constants that are available. In microwave or GHz frequencies signal propagation depends mainly on the waveguide character of the circuitry and consequently only such high dielectric constant materials allow significant miniaturization, permitting the use of narrower conductor line widths and shorter lengths. For example, coaxial dielectric resonators, at this time used in more than 25 million cellular telephones worldwide, could be reduced in size and weight by more than half and in cost by more than two thirds if the dielectric constant of the substrate material could be raised from the present value of alumina of about 9 to over 400 and its dielectric loss (loss tangent) kept below 0.0005.
- It is possible with these processes to fabricate composite materials in which the powdered filler material is a tailored blend of two or more individual materials. The requirements for substrate materials, especially for very high frequency applications, are very exacting, requiring consideration of a large number of physical properties including filler material content, bulk density (range), surface finish, grain size (average), water absorption(%), flexural strength, modulus of elasticity, coefficient of linear thermal expansion, thermal conductivity, dielectric strength, dielectric constant, dissipation factor, and volume resistivity. The possibility of such blending makes it possible to tailor the properties of the substrates to their specific tasks in a manner which is not possible with a sintered ceramic as in most cases the sintering phase rules would be violated and the resulting fired material would fall apart. One of the main reasons for combining filler materials in any given ratio is to obtain a mixture with a tailored dielectric constant, which constant will remain uniform over a temperature range from say −50° C. to +200° C., and with a very high Q factor (equivalent to a very low loss tangent) desirably above 500 and if possible as high as 5,000.
Claims (25)
Priority Applications (14)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/345,813 US6391082B1 (en) | 1999-07-02 | 1999-07-02 | Composites of powdered fillers and polymer matrix |
AT00945027T ATE283305T1 (en) | 1999-07-02 | 2000-07-01 | COMPOSITES MADE OF POWDERIZED FILLERS AND A POLYMER MATRIX AND METHOD FOR THEIR PRODUCTION |
KR1020027000031A KR100690110B1 (en) | 1999-07-02 | 2000-07-01 | Composites of powdered fillers and polymer matrix and process for preparing them |
CNB008119147A CN1175033C (en) | 1999-07-02 | 2000-07-01 | Composite of powdered fillers and polymer matrix and process for preparing them |
PCT/US2000/018038 WO2001002468A1 (en) | 1999-07-02 | 2000-07-01 | Composites of powdered fillers and polymer matrix and process for preparing them |
JP2001508252A JP2003521566A (en) | 1999-07-02 | 2000-07-01 | Composite article comprising a powder filler and a polymer matrix and a method for forming such a composite article |
DE60016228T DE60016228T2 (en) | 1999-07-02 | 2000-07-01 | COMPOUNDS OF POWDERED FILLERS AND A POLYMERMERMATRIX AND METHOD FOR THE PRODUCTION THEREOF |
EP00945027A EP1200509B1 (en) | 1999-07-02 | 2000-07-01 | Composites of powdered fillers and polymer matrix and process for preparing them |
AU59023/00A AU5902300A (en) | 1999-07-02 | 2000-07-01 | Composites of powdered fillers and polymer matrix and process for preparing them |
US09/853,448 US6723999B2 (en) | 1999-07-02 | 2001-05-10 | Electromagnetic wave assisted chemical processing |
US09/894,996 US6742774B2 (en) | 1999-07-02 | 2001-06-27 | Process for high shear gas-liquid reactions |
US09/973,347 US6652805B2 (en) | 1999-07-02 | 2001-10-05 | Highly filled composites of powdered fillers and polymer matrix |
US10/857,295 US7538237B2 (en) | 1999-07-02 | 2004-05-28 | Process for high shear gas-liquid reactions |
US10/857,305 US6994330B2 (en) | 1999-07-02 | 2004-05-28 | Process for high shear gas-liquid reactions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/345,813 US6391082B1 (en) | 1999-07-02 | 1999-07-02 | Composites of powdered fillers and polymer matrix |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/802,037 Continuation-In-Part US6471392B1 (en) | 1999-07-02 | 2001-03-07 | Methods and apparatus for materials processing |
Related Child Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/802,037 Continuation-In-Part US6471392B1 (en) | 1999-07-02 | 2001-03-07 | Methods and apparatus for materials processing |
US09/853,448 Continuation-In-Part US6723999B2 (en) | 1999-07-02 | 2001-05-10 | Electromagnetic wave assisted chemical processing |
US09/894,996 Continuation-In-Part US6742774B2 (en) | 1999-07-02 | 2001-06-27 | Process for high shear gas-liquid reactions |
US09/973,347 Continuation-In-Part US6652805B2 (en) | 1999-07-02 | 2001-10-05 | Highly filled composites of powdered fillers and polymer matrix |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020038582A1 true US20020038582A1 (en) | 2002-04-04 |
US6391082B1 US6391082B1 (en) | 2002-05-21 |
Family
ID=23356603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/345,813 Expired - Lifetime US6391082B1 (en) | 1999-07-02 | 1999-07-02 | Composites of powdered fillers and polymer matrix |
Country Status (9)
Country | Link |
---|---|
US (1) | US6391082B1 (en) |
EP (1) | EP1200509B1 (en) |
JP (1) | JP2003521566A (en) |
KR (1) | KR100690110B1 (en) |
CN (1) | CN1175033C (en) |
AT (1) | ATE283305T1 (en) |
AU (1) | AU5902300A (en) |
DE (1) | DE60016228T2 (en) |
WO (1) | WO2001002468A1 (en) |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020027262A1 (en) * | 2000-04-24 | 2002-03-07 | Park Chan Eon | Low dielectric composite with nano magnetic particles, manufacturing method thereof, and semiconductor device and optical device using the same |
US20030066624A1 (en) * | 2001-09-13 | 2003-04-10 | Holl Richard A. | Methods and apparatus for transfer of heat energy between a body surface and heat transfer fluid |
US20040013587A1 (en) * | 2002-07-16 | 2004-01-22 | Holl Richard A. | Processes employing multiple successive chemical reaction process steps and apparatus therefore |
US20040052158A1 (en) * | 2002-09-11 | 2004-03-18 | Holl Richard A. | Methods and apparatus for high-shear mixing and reacting of materials |
US20040094840A1 (en) * | 2001-03-28 | 2004-05-20 | Hitoshi Sakamoto | Integrated circuit structure |
US6742774B2 (en) | 1999-07-02 | 2004-06-01 | Holl Technologies Company | Process for high shear gas-liquid reactions |
US6752529B2 (en) | 2001-03-07 | 2004-06-22 | Holl Technologies Company | Methods and apparatus for materials processing |
US6787246B2 (en) | 2001-10-05 | 2004-09-07 | Kreido Laboratories | Manufacture of flat surfaced composites comprising powdered fillers in a polymer matrix |
US6830806B2 (en) | 2001-04-12 | 2004-12-14 | Kreido Laboratories | Methods of manufacture of electric circuit substrates and components having multiple electric characteristics and substrates and components so manufactured |
US20050033069A1 (en) * | 1999-07-02 | 2005-02-10 | Holl Richard A. | Process for high shear gas-liquid reactions |
US6938687B2 (en) | 2002-10-03 | 2005-09-06 | Holl Technologies Company | Apparatus for transfer of heat energy between a body surface and heat transfer fluid |
US20060062938A1 (en) * | 2004-09-17 | 2006-03-23 | Sumitomo Chemical Company, Limited | Optical laminate |
US20080103036A1 (en) * | 2006-10-26 | 2008-05-01 | Boessneck Douglas S | Low dielectric glass fiber |
WO2012077846A1 (en) * | 2010-12-06 | 2012-06-14 | 한국세라믹기술원 | High strength organic/inorganic composite having mineral bridge structure, and preparation method thereof |
WO2015034579A1 (en) * | 2013-09-05 | 2015-03-12 | Henkel IP & Holding GmbH | Metal sintering film compositions |
US20150289368A1 (en) * | 2014-04-08 | 2015-10-08 | Finisar Corporation | Hybrid printed circuit board construction |
US20160102109A1 (en) * | 2013-05-30 | 2016-04-14 | Sumitomo Bakelite Co., Ltd. | Hydrophobic inorganic particles, resin composition for heat dissipation member, and electronic component device |
US10000670B2 (en) | 2012-07-30 | 2018-06-19 | Henkel IP & Holding GmbH | Silver sintering compositions with fluxing or reducing agents for metal adhesion |
IT201900010080A1 (en) * | 2019-06-26 | 2020-12-26 | Nol Tec Europe S R L | EQUIPMENT AND PROCEDURE FOR MIXING GRANULATES AND / OR POWDERS AND / OR LIQUIDS IN RUBBER PRODUCTION PLANTS |
CN114016333A (en) * | 2021-11-24 | 2022-02-08 | 泉州市环球新材料科技有限公司 | Thermal bonding method dust-free puffed paper and preparation device thereof |
US11745294B2 (en) | 2015-05-08 | 2023-09-05 | Henkel Ag & Co., Kgaa | Sinterable films and pastes and methods for use thereof |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3664094B2 (en) * | 2000-10-18 | 2005-06-22 | 株式会社村田製作所 | Composite dielectric molded product, manufacturing method thereof, and lens antenna using the same |
DE10224377B4 (en) * | 2002-06-01 | 2004-11-11 | Rauschert Gmbh | Process for the production of pre-ceramic composite bodies with inserts made of steel or cast iron |
US20040236009A1 (en) * | 2003-05-23 | 2004-11-25 | Robson Mafoti | Low density adhesives and sealants |
US20050080185A1 (en) * | 2003-10-10 | 2005-04-14 | Mhetar Vijay R. | Poly(arylene ether) composition and method of making |
US20050110168A1 (en) * | 2003-11-20 | 2005-05-26 | Texas Instruments Incorporated | Low coefficient of thermal expansion (CTE) semiconductor packaging materials |
US7192116B2 (en) * | 2003-11-26 | 2007-03-20 | Fuji Xerox Co., Ltd. | Systems and methods for dissipating heat from a fluid ejector carriage |
US7261389B2 (en) * | 2003-11-26 | 2007-08-28 | Fuji Xerox Co., Ltd. | Systems and methods for dissipating heat into a fluid ejector carriage device |
EP1674151B1 (en) * | 2004-12-23 | 2008-04-16 | Kinematica Ag | Apparatus for dispersion of a solid, liquid or gaseous substance in a liquid |
DE102007010271B4 (en) * | 2007-03-02 | 2014-05-22 | Siemens Aktiengesellschaft | Process for the preparation of mica mica particles and their use |
JP5713894B2 (en) | 2008-07-03 | 2015-05-07 | エイチ アール ディー コーポレーション | Method and apparatus for producing aerated fuel |
US9399143B2 (en) * | 2008-10-31 | 2016-07-26 | Medtronic, Inc. | Antenna for implantable medical devices formed on extension of RF circuit substrate and method for forming the same |
US8497804B2 (en) * | 2008-10-31 | 2013-07-30 | Medtronic, Inc. | High dielectric substrate antenna for implantable miniaturized wireless communications and method for forming the same |
US8983618B2 (en) * | 2008-10-31 | 2015-03-17 | Medtronic, Inc. | Co-fired multi-layer antenna for implantable medical devices and method for forming the same |
US20100140222A1 (en) * | 2008-12-10 | 2010-06-10 | Sun Jennifer Y | Filled polymer composition for etch chamber component |
US8050771B2 (en) * | 2008-12-29 | 2011-11-01 | Medtronic, Inc. | Phased array cofire antenna structure and method for operating the same |
US8626310B2 (en) * | 2008-12-31 | 2014-01-07 | Medtronic, Inc. | External RF telemetry module for implantable medical devices |
US8725263B2 (en) * | 2009-07-31 | 2014-05-13 | Medtronic, Inc. | Co-fired electrical feedthroughs for implantable medical devices having a shielded RF conductive path and impedance matching |
US8419405B2 (en) * | 2009-09-23 | 2013-04-16 | Revolutionary Plastics, Llc | System for forming a composition with an optimized filler |
WO2012166651A2 (en) | 2011-05-27 | 2012-12-06 | Revolutionary Plastics, Llc | Method to heuristically control formation and properties of a composition |
CA2898125A1 (en) | 2011-11-29 | 2013-06-06 | Revolutionary Plastics, Llc | Low density high impact resistant composition and method of forming |
WO2015129574A1 (en) * | 2014-02-26 | 2015-09-03 | 日本碍子株式会社 | Insulating substrate having through-hole |
EP3132497A4 (en) * | 2014-04-18 | 2018-04-18 | TransSiP UK, Ltd. | Metamaterial substrate for circuit design |
DE102015100863B4 (en) | 2015-01-21 | 2022-03-03 | Infineon Technologies Ag | Method of handling a product substrate and a bonded substrate system |
US10116018B2 (en) * | 2016-01-07 | 2018-10-30 | GM Global Technology Operations LLC | Cure in place thermal interface material |
CN108856661B (en) * | 2018-08-09 | 2023-11-03 | 辽宁科技大学 | Production method of crystallizer copper plate on inner wall of groove of continuous casting machine and electroplating bath structure adopted by production method |
US20220348813A1 (en) * | 2019-09-23 | 2022-11-03 | Amogreentech Co., Ltd. | Rf heat dissipation plastic, method for manufacturing rf heat dissipation plastic, and repeater cabinet using same |
US20220340802A1 (en) * | 2019-09-23 | 2022-10-27 | Amogreentech Co., Ltd. | Rf heat dissipation plasitc and repeater cabinet implemented by including same |
DE102021112544A1 (en) | 2021-05-14 | 2022-11-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung eingetragener Verein | Process for producing a fiber-reinforced plastic product and plant therefor |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5279463A (en) * | 1992-08-26 | 1994-01-18 | Holl Richard A | Methods and apparatus for treating materials in liquids |
US5658994A (en) * | 1995-07-13 | 1997-08-19 | Air Products And Chemicals, Inc. | Nonfunctionalized poly(arylene ether) dielectrics |
US5874516A (en) * | 1995-07-13 | 1999-02-23 | Air Products And Chemicals, Inc. | Nonfunctionalized poly(arylene ethers) |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4287075A (en) | 1978-04-17 | 1981-09-01 | Tdk Electronics Co., Ltd. | High dielectric constant type ceramic composition consisting essentially of Pb(Fe1/2 Nb1/2)O3 -Pb(Mg1/3 Nb2/3)O3 -Pb(Mg1/2 W1/2)O3 |
US4335180A (en) | 1978-12-26 | 1982-06-15 | Rogers Corporation | Microwave circuit boards |
JPS62121758A (en) * | 1985-08-26 | 1987-06-03 | Matsushita Electric Works Ltd | Polyphenylene oxide resin composition and sheet composed of said resin composition |
DE3774390D1 (en) * | 1986-09-22 | 1991-12-12 | Gen Electric | CURTAINABLE LINEAR POLYPHENYLENE ETHER RESIN COMPOSITIONS CONTAINING POLYMERS WITH POLYMERIC STRENGTHS THAT INTERRUPT ITSELF AND METHOD. |
DE3725058A1 (en) | 1987-07-29 | 1989-02-09 | Roehm Gmbh | THERMOPLASTICALLY PROCESSABLE POLYARYLENETHER WITH 9,9-BIS (4'-HYDROXYPHENYL) FLUORINE |
JP2844233B2 (en) * | 1988-12-26 | 1999-01-06 | 日本ジーイープラスチックス株式会社 | Polyphenylene ether resin composition |
EP0388358B1 (en) | 1989-03-17 | 1996-09-25 | Sumitomo Chemical Company Limited | Polyarylene ether |
US5198137A (en) * | 1989-06-12 | 1993-03-30 | Hoeganaes Corporation | Thermoplastic coated magnetic powder compositions and methods of making same |
JPH03179805A (en) | 1989-12-07 | 1991-08-05 | Murata Mfg Co Ltd | Composite material for dielectric lens antenna |
US5204416A (en) | 1990-04-17 | 1993-04-20 | Raychem Corporation | Crosslinked fluorinated poly(arylene ether) |
US5506049C1 (en) | 1991-05-24 | 2001-05-29 | World Properties Inc | Particulate filled composite film and method of making same |
US5268140A (en) * | 1991-10-03 | 1993-12-07 | Hoeganaes Corporation | Thermoplastic coated iron powder components and methods of making same |
US5391603A (en) | 1992-03-09 | 1995-02-21 | The Dow Chemical Company | Impact modified syndiotactic vinyl aromatic polymers |
EP0571883A1 (en) | 1992-05-26 | 1993-12-01 | Hoechst Aktiengesellschaft | Polyarylethers with xanthone units, method for their production and their application |
US5449652A (en) | 1993-06-04 | 1995-09-12 | Battelle Memorial Institute | Ceramic compositions for BZN dielectric resonators |
US5358775A (en) | 1993-07-29 | 1994-10-25 | Rogers Corporation | Fluoropolymeric electrical substrate material exhibiting low thermal coefficient of dielectric constant |
DE4344044A1 (en) * | 1993-12-23 | 1995-06-29 | Abb Research Ltd | Electrical insulation material and method for producing an electrically insulated conductor |
SE9402497D0 (en) * | 1994-07-18 | 1994-07-18 | Hoeganaes Ab | Iron powder components containing thermoplastic resin and methods of making the same |
US5552210A (en) | 1994-11-07 | 1996-09-03 | Rogers Corporation | Ceramic filled composite polymeric electrical substrate material exhibiting high dielectric constant and low thermal coefficient of dielectric constant |
US5693742A (en) | 1994-12-01 | 1997-12-02 | General Electric Company | Solventless method for making polyarylene ethers |
DE19526855A1 (en) | 1995-07-22 | 1997-01-23 | Basf Ag | Process for the preparation of polyarylene ethers with anhydride end groups |
DE19530574A1 (en) | 1995-08-19 | 1997-02-20 | Basf Ag | Titanium dioxide pigments |
US5658485A (en) | 1995-10-03 | 1997-08-19 | Lucent Technologies Inc. | Pyrochlore based oxides with high dielectric constant and low temperature coefficient |
US5659006A (en) | 1995-12-14 | 1997-08-19 | General Electric Company | Method for making polyarylene ethers from mesitol |
US5739193A (en) | 1996-05-07 | 1998-04-14 | Hoechst Celanese Corp. | Polymeric compositions having a temperature-stable dielectric constant |
US5929138A (en) | 1996-11-05 | 1999-07-27 | Raychem Corporation | Highly thermally conductive yet highly comformable alumina filled composition and method of making the same |
US6039784A (en) * | 1997-03-12 | 2000-03-21 | Hoeganaes Corporation | Iron-based powder compositions containing green strength enhancing lubricants |
US6143052A (en) * | 1997-07-03 | 2000-11-07 | Kiyokawa Plating Industries, Co., Ltd. | Hydrogen storage material |
JPH11322920A (en) | 1998-05-19 | 1999-11-26 | Asahi Chem Ind Co Ltd | Highly adhesive polyarylene ether |
US6093636A (en) | 1998-07-08 | 2000-07-25 | International Business Machines Corporation | Process for manufacture of integrated circuit device using a matrix comprising porous high temperature thermosets |
-
1999
- 1999-07-02 US US09/345,813 patent/US6391082B1/en not_active Expired - Lifetime
-
2000
- 2000-07-01 KR KR1020027000031A patent/KR100690110B1/en not_active IP Right Cessation
- 2000-07-01 AT AT00945027T patent/ATE283305T1/en not_active IP Right Cessation
- 2000-07-01 AU AU59023/00A patent/AU5902300A/en not_active Abandoned
- 2000-07-01 DE DE60016228T patent/DE60016228T2/en not_active Expired - Fee Related
- 2000-07-01 JP JP2001508252A patent/JP2003521566A/en active Pending
- 2000-07-01 WO PCT/US2000/018038 patent/WO2001002468A1/en active IP Right Grant
- 2000-07-01 EP EP00945027A patent/EP1200509B1/en not_active Expired - Lifetime
- 2000-07-01 CN CNB008119147A patent/CN1175033C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5279463A (en) * | 1992-08-26 | 1994-01-18 | Holl Richard A | Methods and apparatus for treating materials in liquids |
US5538191A (en) * | 1992-08-26 | 1996-07-23 | Holl; Richard A. | Methods and apparatus for high-shear material treatment |
US5658994A (en) * | 1995-07-13 | 1997-08-19 | Air Products And Chemicals, Inc. | Nonfunctionalized poly(arylene ether) dielectrics |
US5874516A (en) * | 1995-07-13 | 1999-02-23 | Air Products And Chemicals, Inc. | Nonfunctionalized poly(arylene ethers) |
Non-Patent Citations (1)
Title |
---|
P. 42 of Materials and Processes for Microwave Hybrids , by Richard Brown, published 1989 by International Society for Hybrid Microelectronis, Reston VA ( See p. 2, lines of this application) * |
Cited By (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6994330B2 (en) | 1999-07-02 | 2006-02-07 | Kriedo Laboratories | Process for high shear gas-liquid reactions |
US7538237B2 (en) | 1999-07-02 | 2009-05-26 | Kreido Laboratories | Process for high shear gas-liquid reactions |
US20050033069A1 (en) * | 1999-07-02 | 2005-02-10 | Holl Richard A. | Process for high shear gas-liquid reactions |
US6742774B2 (en) | 1999-07-02 | 2004-06-01 | Holl Technologies Company | Process for high shear gas-liquid reactions |
US6849926B2 (en) * | 2000-04-24 | 2005-02-01 | Pohang University Of Science And Technology Foundation | Low dielectric constant composite material containing nano magnetic particles, and optical and semiconductor devices using the low dielectric constant composite material |
US20020027262A1 (en) * | 2000-04-24 | 2002-03-07 | Park Chan Eon | Low dielectric composite with nano magnetic particles, manufacturing method thereof, and semiconductor device and optical device using the same |
US6752529B2 (en) | 2001-03-07 | 2004-06-22 | Holl Technologies Company | Methods and apparatus for materials processing |
US20040094840A1 (en) * | 2001-03-28 | 2004-05-20 | Hitoshi Sakamoto | Integrated circuit structure |
US6830806B2 (en) | 2001-04-12 | 2004-12-14 | Kreido Laboratories | Methods of manufacture of electric circuit substrates and components having multiple electric characteristics and substrates and components so manufactured |
US20030066624A1 (en) * | 2001-09-13 | 2003-04-10 | Holl Richard A. | Methods and apparatus for transfer of heat energy between a body surface and heat transfer fluid |
US6787246B2 (en) | 2001-10-05 | 2004-09-07 | Kreido Laboratories | Manufacture of flat surfaced composites comprising powdered fillers in a polymer matrix |
US20060245991A1 (en) * | 2002-07-16 | 2006-11-02 | Kreido Laboratories | Processes Employing Multiple Successive Chemical Reaction Process Steps and Apparatus Therefore |
US7575728B2 (en) | 2002-07-16 | 2009-08-18 | Kreido Laboratories | Processes employing multiple successive chemical reaction process steps and apparatus therefore |
US20040013587A1 (en) * | 2002-07-16 | 2004-01-22 | Holl Richard A. | Processes employing multiple successive chemical reaction process steps and apparatus therefore |
US7098360B2 (en) | 2002-07-16 | 2006-08-29 | Kreido Laboratories | Processes employing multiple successive chemical reaction process steps and apparatus therefore |
US7165881B2 (en) | 2002-09-11 | 2007-01-23 | Holl Technologies Corporation | Methods and apparatus for high-shear mixing and reacting of materials |
US20040052158A1 (en) * | 2002-09-11 | 2004-03-18 | Holl Richard A. | Methods and apparatus for high-shear mixing and reacting of materials |
US6938687B2 (en) | 2002-10-03 | 2005-09-06 | Holl Technologies Company | Apparatus for transfer of heat energy between a body surface and heat transfer fluid |
US20060062938A1 (en) * | 2004-09-17 | 2006-03-23 | Sumitomo Chemical Company, Limited | Optical laminate |
US7695782B2 (en) * | 2004-09-17 | 2010-04-13 | Sumitomo Chemical Company, Limited | Optical laminate |
KR101104130B1 (en) | 2006-10-26 | 2012-01-13 | 에이지와이 홀딩 코포레이션 | Low dielectric glass fiber |
US7678721B2 (en) | 2006-10-26 | 2010-03-16 | Agy Holding Corp. | Low dielectric glass fiber |
WO2008052154A3 (en) * | 2006-10-26 | 2008-06-19 | Agy Holding Corp | Low dielectric glass fiber |
US20110042129A1 (en) * | 2006-10-26 | 2011-02-24 | Agy Holding Corp. | Low dielectric glass fiber |
US20080103036A1 (en) * | 2006-10-26 | 2008-05-01 | Boessneck Douglas S | Low dielectric glass fiber |
WO2012077846A1 (en) * | 2010-12-06 | 2012-06-14 | 한국세라믹기술원 | High strength organic/inorganic composite having mineral bridge structure, and preparation method thereof |
US10000670B2 (en) | 2012-07-30 | 2018-06-19 | Henkel IP & Holding GmbH | Silver sintering compositions with fluxing or reducing agents for metal adhesion |
US20160102109A1 (en) * | 2013-05-30 | 2016-04-14 | Sumitomo Bakelite Co., Ltd. | Hydrophobic inorganic particles, resin composition for heat dissipation member, and electronic component device |
WO2015034579A1 (en) * | 2013-09-05 | 2015-03-12 | Henkel IP & Holding GmbH | Metal sintering film compositions |
US20150289368A1 (en) * | 2014-04-08 | 2015-10-08 | Finisar Corporation | Hybrid printed circuit board construction |
US9526185B2 (en) * | 2014-04-08 | 2016-12-20 | Finisar Corporation | Hybrid PCB with multi-unreinforced laminate |
US11745294B2 (en) | 2015-05-08 | 2023-09-05 | Henkel Ag & Co., Kgaa | Sinterable films and pastes and methods for use thereof |
IT201900010080A1 (en) * | 2019-06-26 | 2020-12-26 | Nol Tec Europe S R L | EQUIPMENT AND PROCEDURE FOR MIXING GRANULATES AND / OR POWDERS AND / OR LIQUIDS IN RUBBER PRODUCTION PLANTS |
WO2020261143A1 (en) * | 2019-06-26 | 2020-12-30 | Nte Holding S.R.L. | Apparatus and process for mixing granules and/or powders and/or liquids in rubber production plants |
CN114016333A (en) * | 2021-11-24 | 2022-02-08 | 泉州市环球新材料科技有限公司 | Thermal bonding method dust-free puffed paper and preparation device thereof |
Also Published As
Publication number | Publication date |
---|---|
DE60016228D1 (en) | 2004-12-30 |
EP1200509A1 (en) | 2002-05-02 |
AU5902300A (en) | 2001-01-22 |
JP2003521566A (en) | 2003-07-15 |
CN1175033C (en) | 2004-11-10 |
DE60016228T2 (en) | 2006-05-04 |
US6391082B1 (en) | 2002-05-21 |
ATE283305T1 (en) | 2004-12-15 |
WO2001002468A9 (en) | 2002-07-25 |
KR100690110B1 (en) | 2007-03-08 |
CN1420904A (en) | 2003-05-28 |
EP1200509B1 (en) | 2004-11-24 |
WO2001002468A1 (en) | 2001-01-11 |
KR20020085865A (en) | 2002-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6391082B1 (en) | Composites of powdered fillers and polymer matrix | |
US6652805B2 (en) | Highly filled composites of powdered fillers and polymer matrix | |
US5739193A (en) | Polymeric compositions having a temperature-stable dielectric constant | |
US6787246B2 (en) | Manufacture of flat surfaced composites comprising powdered fillers in a polymer matrix | |
WO2001082311A1 (en) | Dielectric ceramic, resin-ceramics composite, and electric parts and antenna and method for their manufacture | |
CN109661111A (en) | Flexible copper-clad plate and preparation method thereof based on liquid crystal polymer film | |
EP3748654A1 (en) | Insulation sheet, laminate, and substrate | |
CN101155470A (en) | Insulating material for printed circuit board | |
CN113211903A (en) | Production method of ceramic-filled type hydrocarbon resin copper-clad plate | |
EP0868732A1 (en) | Poly(phenylene sulfide) composites having a high dielectric constant | |
JP2002344100A (en) | Dielectric material for substrate, and manufacturing method therefor | |
JP2007048703A (en) | Composite dielectric material and prepreg using this, metal foil coated object, molding body, composite dielectric substrate, and multilayer substrate | |
US4784893A (en) | Heat conductive circuit board and method for manufacturing the same | |
WO1998021272A2 (en) | Manufacture of composites of inorganic powder and polymer materials | |
CN112166158B (en) | Composite particles and method for producing same | |
JPH0786153B2 (en) | Method for producing porous sheet and method for producing substrate using the same | |
CN114434911B (en) | High-heat-conductivity high-frequency flexible copper-clad plate and preparation method thereof | |
CN109336461A (en) | A kind of PTFE base microwave composite medium substrate and preparation method thereof | |
JPH0660719A (en) | Composite dielectric | |
JPH05167211A (en) | Laminated board for printed circuit and manufacture thereof | |
JP3938299B2 (en) | Non-sintered sheet and manufacturing method thereof | |
JPH06106629A (en) | Manufacture of sheet-shaped material | |
JPH07162113A (en) | Laminated board for printed circuit | |
JPH03216910A (en) | Composite dielectric and manufacture thereof | |
JP2002053680A (en) | Composite dielectric substrate and prepreg |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HOLL TECHNOLOGIES COMPANY, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HOLL, RICHARD A.;REEL/FRAME:011034/0073 Effective date: 20000724 |
|
DJ | All references should be deleted, no patent was granted | ||
WDR | Patent withdrawn according to listing issued by the uspto on prs-date | ||
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
AS | Assignment |
Owner name: KREIDO BIOFUELS, INC., CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HOLL TECHNOLOGIES, INC.;REEL/FRAME:018837/0524 Effective date: 20070201 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |
|
AS | Assignment |
Owner name: FOUR RIVERS BIOENERGY COMPANY, INC., KENTUCKY Free format text: NUNC PRO TUNC ASSIGNMENT;ASSIGNOR:KREIDO BIOFUELS, INC.;REEL/FRAME:030974/0137 Effective date: 20090303 |
|
AS | Assignment |
Owner name: BLUE NORTHERN ENERGY, LLC, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FOUR RIVERS BIOENERGY COMPANY, INC.;REEL/FRAME:031153/0284 Effective date: 20130423 |
|
AS | Assignment |
Owner name: VERSUM MATERIALS US, LLC, ARIZONA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:AIR PRODUCTS AND CHEMICALS, INC.;REEL/FRAME:041772/0733 Effective date: 20170214 |
|
AS | Assignment |
Owner name: 323 TRUST, CALIFORNIA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:BLUE NORTHERN ENERGY, LLC;REEL/FRAME:042990/0616 Effective date: 20131129 |