CA1168395A - Molded bodies - Google Patents
Molded bodiesInfo
- Publication number
- CA1168395A CA1168395A CA000351750A CA351750A CA1168395A CA 1168395 A CA1168395 A CA 1168395A CA 000351750 A CA000351750 A CA 000351750A CA 351750 A CA351750 A CA 351750A CA 1168395 A CA1168395 A CA 1168395A
- Authority
- CA
- Canada
- Prior art keywords
- molded body
- binding mixture
- body according
- halogen
- chlorinated
- 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.)
- Expired
Links
Classifications
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/02—Halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- 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
- C08J2321/00—Characterised by the use of unspecified rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Molded bodies of elastomeric macro-molecular material with a direct binding mixture serving for producing A
bonding connection with metallic or other rigid materials during polymerization or vulcanization of the macro-molecules. The binding mixture contains substances which liberate halogen or hydrogen halides.
Molded bodies of elastomeric macro-molecular material with a direct binding mixture serving for producing A
bonding connection with metallic or other rigid materials during polymerization or vulcanization of the macro-molecules. The binding mixture contains substances which liberate halogen or hydrogen halides.
Description
The present lnventiQn relates to rnolded bodîes o~
elastomeric macro~molecular material with a direct binding mixture serving for produoing a bonding connection with metals or other rigid m~terials during polymerization or vulcani~a~ion of lthe macro~fnoleel1les.
In the production of molded bodies of rubber or synthetic material of all types s~rith metallic re~nforcing inserts or layers, for exarnple oiE conv~yor belts wî~h longîtudinally ex'cending embedded steel wire c~bles7 it has 10 been known for a long tîme aI~d .is common practice to use so-called "direct-bindîng'l mixtures fox producing the necessary adhering binding of the rein~orcing ~lements to the elastomeric material during the vulc~ization or psly-m~rizati-~n accomp~:nying ~he fînal shaping. The durabîlity of ~he coxmection îs ~he decisîve factor :~r the service~
ability or function value of the finished molded bodi~s;
thîs durability is determ~ned essentially by two parameters~
n~mel~, orl the one hand, the quality o ~che îni~cial bondîng attainable wi h the ~rea'cment process arld~ on ~he o~her 20 harld ~ by the aging behavior of ~he connection , i . e ., ~he gradual abatement or subsiding of khe honding orces. ~ile the initial bonding primarily depends upon the par.i~ular utiliæed base polymer, still other effects exîst ~ich in"
fluen-~ each other or superimpose upon each other for the aging ~ehavior. Asîde from the actual connectîon itself "
the polymer îs al~o subjected to the influence of aging, and -- 1 ~
~` ' !
. ; ' as a cons~quence thereof9 the binding half in he boundary layer nex~ to ~he me~al ls at~acked in time.
The difficulties in producing a highly loadable or stressable and durable binding connection are still further incrcased by the fact that the initial bonding and aging behavinr for pol~ners of dif~erent types c~n be of entirely differen~ importanceO Th~s, or example, for the so-called all-purpose-rubhers, lik~ natural ~nd styrene~b~tadieDe r~bber, the deterioration of the connec~ion by aging is in the foreground, while, in contrast, for example for nitrile~
butadiene rubber or for other sp~cial ~ubbers, o~ the other hand, a satisfactory ini~ial bonding c~n be at~ained ~nly wqth difficulties.
Accordingly, the object o the present invention is to attain a consider~bly irnproved bonding for both phases, in~
dependently of the characteristic of the base polymer~ This objec~- of the present invention goes :Ear beyond the possi~
bilities ofered by ~he kno~ gal~anizing (~inc pla~ing~, brass plating, or bronzing of the metallic parts with other ; 20 surface treatmentsO
By one aspect of thi~ inv~ntion, there is provided a molded body, of ~n elastomeric material, whi~h comprises a direct binding mixture containing halogen or hydrogen halide releasing materials for pro~ucing a bonding connection of elastomeric mat:erial with metallic or other rigid materials during polymeri.zation or vulc~ni~ation of the elastomeric ~ 2 -, ~
material; saîd binding mîxture conkaining at least ~e .su~
st~nc~ which liberates material selected from the group con~
- sisting o~ halogeDs and hydrogen halides as halogen sources for such elast~meric material including all purpose rubbers, like natural and poly~utadiene, styrene-butadiene9 poly~
chloroprene, nitrile rubber, and nitrile-butad:iene rubber.
Improvements in the initi~1 bondi~g by frqm 10% to 20% are thus possiblet while simul~aneously the lo.sses in strength of the general purpose rubbers d~e to aging can be 10 practically completely suppressed7 and in pa~t ran be re-versed into the opposite in comparison to the ini~.ial bonding.
Liqu~d chloriDated paraffins, especially with a chlor-ine proportion of approximately 70V/o~ bromina~.ed phenol resins, and chlorinated polyethylenes, poss~y also in com~
bination with each other~ as well as chlorinat~d rubber, have proven themselves suitable ~s halogen sources. Undesired overrea~tions are expediently precluded by the addition of magnesium oxide or other s~abilizing substances. The scope of the prese~t i~vention also includes the further addition to the binding mixture o halogen in a proportional ratio ranging be~ween 0.7/0 to 15~/o~ preferably rom 2% to 7%O
The teaching o the present invention is clarified still ~urther by the following listing of several mix~.ure examples and of th~ test results at~ained ~herewi~h~ In all GaSes~ direct binding mixtures are involYed on differen~
rubber bases, on the one hand wi~h ~he ad~ition of halogen ~ 3 -~6J~
( Column a), ~3nd on the other hand without the addition of halogen (Col~ b)o Galv~nized steel ~ire cables o:f 4 rnm diameter were vulcanized into the mixtures produced in a conventional manner in an internal mixer, and thereafter, respectively a~tler an aging period of 22S minutes at a temperature of 1~5G, the tearing or pull~out values were determined according to DIN 22 1'31 (German Industrial Norm or Standard 22 131).
- 3a -}~q~j :
ture on Natural R b_ Base a b Shee~s RSS 1 34.4 34.4 Polybut~diene 18.90 18.G0 Magnesium Oxide 205 2.5 Carbon black N660 13.1 1.301 Silicon dioxide 1300 13.0 Hydrocarbon resln 1.2 1~2 Softener 5~0 6.4 Liquid chlorinated paraffin (70~/0 chlorine~ 1.4 Phenolic aging protection mea~s 0.5 0~5 Zinc oxide 4.0 4.0 Lead monoxide 1~0 1~0 Stearic acid 1.0 1.0 Resorcinol 1.5 1.5 ~examethylenete~ramine 0~8 0.8 Benzothiazole-2-sulfenmorpholine 0.~ 0.6 Sulfur 2.0 2 0 . ~
100.~ 1~0.0 - Vulcanlza~ion 35 min. a~ 150'C
Specific welght 1.20 1.19 Strength N~mm 15.5 lS~7 Breaking tension % (elongation a~ break) 564 ~70 Shore A ~ardnless 62 62 Tear~ or pull-out values N~mm fresh 79.5 79.5 aged 94.00 73 00 Mixture on ~ nitri.le ru~ber base a Nltrile R~bber (28~/o ACN) 45.0 45.0 Phenolic aging protect;on means 0.3 0.3 Stearic acid 0~7 0.7 Silicon dioxide 15.S 15~5 Carbon bl~ck N339 .13dO 13.0 Softener 4~0 4.0 Hydrocarb4n resin 5~0 8,0 2inc oxide 5.~ 5.0 Resorcinol 1~5 1~5 Cobalt c~mplex in oil (16% Co) 2,0 2~0 Hex~methylenetetramine 2.0 2.0 Tetramethylthiuram disulfide (thiramj 1.5 1.5 Benzothiazole~2-sulfe~norpholine 1.0 1.0 sulfur 005 0~5 Liquid chlorinated paraff~n (70% chlorine~ 3.0 ___._ 100~ 0 10~. 0 Vulcanization 20 min. at 150C
Specific weight 1027 1.25 Strength N~mm19.5 18.2 Breaki~g ten~ion % (elonga~ion at braak) 637 745 Shore A Hardness 67 64 Tear- or pull-out values Njmm 6003 43~7 _ 5 ~
a b Polychloroprene (Mercaptan~type 50iO 50~0 Magnesium oxide 2.5 2,5 Carbon black N339 14.0 17.0 Stearic acid loO 1,0 Softener - 7.0 Aminic aging protection means 1.0 1.0 Zinc oxid~ 7.75 7.75 Chalk fli~t lO.0 10~0 Cobalt c~mplex in oil (16% Co) 2.5 2.5 Tetramet~yl~h~uram disulfide Sthiram) 005 0.5 Diortho-tol~yl-Gu~idine 0.2$ 0.25 Sulfur 0.5 005 Liquid chlorinated paraffin ~70% chlorine) lO.0 . 0 Vulcanization 40 min~ at 160C
Specific weight 1~52 1047 Stre~gth N~mm 17~7 17.9 Breaking tension % (elongation ~ break) 428 409 Shore A hardness 68 70 Tear~ or pull-out values N/mm 10207 90~0 qj The present inventioII is, of course, in no wa,v re-st~icted to the 5p~3cif ic disclosure of the speci:Eication and examples9but also encompasses any modi~ications within the scope of ~he apper~ed claims,,
elastomeric macro~molecular material with a direct binding mixture serving for produoing a bonding connection with metals or other rigid m~terials during polymerization or vulcani~a~ion of lthe macro~fnoleel1les.
In the production of molded bodies of rubber or synthetic material of all types s~rith metallic re~nforcing inserts or layers, for exarnple oiE conv~yor belts wî~h longîtudinally ex'cending embedded steel wire c~bles7 it has 10 been known for a long tîme aI~d .is common practice to use so-called "direct-bindîng'l mixtures fox producing the necessary adhering binding of the rein~orcing ~lements to the elastomeric material during the vulc~ization or psly-m~rizati-~n accomp~:nying ~he fînal shaping. The durabîlity of ~he coxmection îs ~he decisîve factor :~r the service~
ability or function value of the finished molded bodi~s;
thîs durability is determ~ned essentially by two parameters~
n~mel~, orl the one hand, the quality o ~che îni~cial bondîng attainable wi h the ~rea'cment process arld~ on ~he o~her 20 harld ~ by the aging behavior of ~he connection , i . e ., ~he gradual abatement or subsiding of khe honding orces. ~ile the initial bonding primarily depends upon the par.i~ular utiliæed base polymer, still other effects exîst ~ich in"
fluen-~ each other or superimpose upon each other for the aging ~ehavior. Asîde from the actual connectîon itself "
the polymer îs al~o subjected to the influence of aging, and -- 1 ~
~` ' !
. ; ' as a cons~quence thereof9 the binding half in he boundary layer nex~ to ~he me~al ls at~acked in time.
The difficulties in producing a highly loadable or stressable and durable binding connection are still further incrcased by the fact that the initial bonding and aging behavinr for pol~ners of dif~erent types c~n be of entirely differen~ importanceO Th~s, or example, for the so-called all-purpose-rubhers, lik~ natural ~nd styrene~b~tadieDe r~bber, the deterioration of the connec~ion by aging is in the foreground, while, in contrast, for example for nitrile~
butadiene rubber or for other sp~cial ~ubbers, o~ the other hand, a satisfactory ini~ial bonding c~n be at~ained ~nly wqth difficulties.
Accordingly, the object o the present invention is to attain a consider~bly irnproved bonding for both phases, in~
dependently of the characteristic of the base polymer~ This objec~- of the present invention goes :Ear beyond the possi~
bilities ofered by ~he kno~ gal~anizing (~inc pla~ing~, brass plating, or bronzing of the metallic parts with other ; 20 surface treatmentsO
By one aspect of thi~ inv~ntion, there is provided a molded body, of ~n elastomeric material, whi~h comprises a direct binding mixture containing halogen or hydrogen halide releasing materials for pro~ucing a bonding connection of elastomeric mat:erial with metallic or other rigid materials during polymeri.zation or vulc~ni~ation of the elastomeric ~ 2 -, ~
material; saîd binding mîxture conkaining at least ~e .su~
st~nc~ which liberates material selected from the group con~
- sisting o~ halogeDs and hydrogen halides as halogen sources for such elast~meric material including all purpose rubbers, like natural and poly~utadiene, styrene-butadiene9 poly~
chloroprene, nitrile rubber, and nitrile-butad:iene rubber.
Improvements in the initi~1 bondi~g by frqm 10% to 20% are thus possiblet while simul~aneously the lo.sses in strength of the general purpose rubbers d~e to aging can be 10 practically completely suppressed7 and in pa~t ran be re-versed into the opposite in comparison to the ini~.ial bonding.
Liqu~d chloriDated paraffins, especially with a chlor-ine proportion of approximately 70V/o~ bromina~.ed phenol resins, and chlorinated polyethylenes, poss~y also in com~
bination with each other~ as well as chlorinat~d rubber, have proven themselves suitable ~s halogen sources. Undesired overrea~tions are expediently precluded by the addition of magnesium oxide or other s~abilizing substances. The scope of the prese~t i~vention also includes the further addition to the binding mixture o halogen in a proportional ratio ranging be~ween 0.7/0 to 15~/o~ preferably rom 2% to 7%O
The teaching o the present invention is clarified still ~urther by the following listing of several mix~.ure examples and of th~ test results at~ained ~herewi~h~ In all GaSes~ direct binding mixtures are involYed on differen~
rubber bases, on the one hand wi~h ~he ad~ition of halogen ~ 3 -~6J~
( Column a), ~3nd on the other hand without the addition of halogen (Col~ b)o Galv~nized steel ~ire cables o:f 4 rnm diameter were vulcanized into the mixtures produced in a conventional manner in an internal mixer, and thereafter, respectively a~tler an aging period of 22S minutes at a temperature of 1~5G, the tearing or pull~out values were determined according to DIN 22 1'31 (German Industrial Norm or Standard 22 131).
- 3a -}~q~j :
ture on Natural R b_ Base a b Shee~s RSS 1 34.4 34.4 Polybut~diene 18.90 18.G0 Magnesium Oxide 205 2.5 Carbon black N660 13.1 1.301 Silicon dioxide 1300 13.0 Hydrocarbon resln 1.2 1~2 Softener 5~0 6.4 Liquid chlorinated paraffin (70~/0 chlorine~ 1.4 Phenolic aging protection mea~s 0.5 0~5 Zinc oxide 4.0 4.0 Lead monoxide 1~0 1~0 Stearic acid 1.0 1.0 Resorcinol 1.5 1.5 ~examethylenete~ramine 0~8 0.8 Benzothiazole-2-sulfenmorpholine 0.~ 0.6 Sulfur 2.0 2 0 . ~
100.~ 1~0.0 - Vulcanlza~ion 35 min. a~ 150'C
Specific welght 1.20 1.19 Strength N~mm 15.5 lS~7 Breaking tension % (elongation a~ break) 564 ~70 Shore A ~ardnless 62 62 Tear~ or pull-out values N~mm fresh 79.5 79.5 aged 94.00 73 00 Mixture on ~ nitri.le ru~ber base a Nltrile R~bber (28~/o ACN) 45.0 45.0 Phenolic aging protect;on means 0.3 0.3 Stearic acid 0~7 0.7 Silicon dioxide 15.S 15~5 Carbon bl~ck N339 .13dO 13.0 Softener 4~0 4.0 Hydrocarb4n resin 5~0 8,0 2inc oxide 5.~ 5.0 Resorcinol 1~5 1~5 Cobalt c~mplex in oil (16% Co) 2,0 2~0 Hex~methylenetetramine 2.0 2.0 Tetramethylthiuram disulfide (thiramj 1.5 1.5 Benzothiazole~2-sulfe~norpholine 1.0 1.0 sulfur 005 0~5 Liquid chlorinated paraff~n (70% chlorine~ 3.0 ___._ 100~ 0 10~. 0 Vulcanization 20 min. at 150C
Specific weight 1027 1.25 Strength N~mm19.5 18.2 Breaki~g ten~ion % (elonga~ion at braak) 637 745 Shore A Hardness 67 64 Tear- or pull-out values Njmm 6003 43~7 _ 5 ~
a b Polychloroprene (Mercaptan~type 50iO 50~0 Magnesium oxide 2.5 2,5 Carbon black N339 14.0 17.0 Stearic acid loO 1,0 Softener - 7.0 Aminic aging protection means 1.0 1.0 Zinc oxid~ 7.75 7.75 Chalk fli~t lO.0 10~0 Cobalt c~mplex in oil (16% Co) 2.5 2.5 Tetramet~yl~h~uram disulfide Sthiram) 005 0.5 Diortho-tol~yl-Gu~idine 0.2$ 0.25 Sulfur 0.5 005 Liquid chlorinated paraffin ~70% chlorine) lO.0 . 0 Vulcanization 40 min~ at 160C
Specific weight 1~52 1047 Stre~gth N~mm 17~7 17.9 Breaking tension % (elongation ~ break) 428 409 Shore A hardness 68 70 Tear~ or pull-out values N/mm 10207 90~0 qj The present inventioII is, of course, in no wa,v re-st~icted to the 5p~3cif ic disclosure of the speci:Eication and examples9but also encompasses any modi~ications within the scope of ~he apper~ed claims,,
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A molded body, of an elastomeric material, which comprises a direct binding mixture containing halogen or hydrogen halide releasing materials for producing a bonding connection of elastomeric, material with metallic or other rigid materials during polymerization or vulcanization of the elastomeric materia,l said binding mixture containing at least one substance which liberates material selected from the group consisting of halogens and hydrogen halides as halogen sources for such elastomeric material including all-purpose rubbers, like natural and polybutadiene, styrene-butadiene, polychloroprene, nitrile rubber, and nitrile-butadiene rubber.
2. A molded body according to claim 1, in which said binding mixture contains at least one substance select-ed from the group consisting of liquid chlorinated paraffins, brominated phenol resins, chlorinated polyethylenes, and chlorinated rubber as halogen sources proven suitable.
3. A molded body according to claim 1, in which said binding mixture for releasing halogens contains liquid chlorinated paraffin having a chlorine content of about 70%.
4. A molded body according to claim 1, in which said binding mixture for releasing halogens contains chlorinated polyethylenes in combination with one of the substances of the group consisting of chlorinated parafins and brominated phenol resins.
5. A molded body according to claim 1, in which said binding mixture for releasing halogens also contains at least one stabilizing substance for preventing over-reactions.
6. A molded body according to claim 5, in which said at least one stabilizing substance for preventing overreactions is magnesium oxide.
7. A molded body according to claim 5, in which said binding mixture additionally includes a halogen con-tent in a range of about 0.7 to 15%.
8. A molded body according to claim 7, in which said halogen content ranges between about 2 to 7%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2919276.5 | 1979-05-12 | ||
| DE19792919276 DE2919276C2 (en) | 1979-05-12 | 1979-05-12 | Process for the production of moldings from an elastomeric macromolecular material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168395A true CA1168395A (en) | 1984-05-29 |
Family
ID=6070621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000351750A Expired CA1168395A (en) | 1979-05-12 | 1980-05-12 | Molded bodies |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS55156042A (en) |
| CA (1) | CA1168395A (en) |
| DE (1) | DE2919276C2 (en) |
| FR (1) | FR2456609B1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2824173C2 (en) * | 1978-06-02 | 1987-04-23 | Continental Gummi-Werke Ag, 3000 Hannover | Laminated body, especially conveyor belt or drive belt |
| US4376838A (en) * | 1981-03-18 | 1983-03-15 | The Firestone Tire & Rubber Company | Cured rubber skim stocks having improved metal adhesion and metal adhesion retention by use of organo-metal complexes and halogenated polymer |
| GB8305229D0 (en) * | 1983-02-25 | 1983-03-30 | Bekaert Sa Nv | Steel fibre reinforced rubber article |
| DE3328848C2 (en) * | 1983-08-10 | 1986-10-02 | Phoenix Ag, 2100 Hamburg | Rubber mixture for connecting metal bodies made of stainless steel with rubber mixtures based on polychloroprene |
| US4480066A (en) * | 1983-08-18 | 1984-10-30 | The Firestone Tire & Rubber Company | Rubber compositions and articles thereof having improved metal adhesion and metal adhesion retention |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3629038A (en) * | 1968-02-07 | 1971-12-21 | Asahi Chemical Ind | Method for bonding rubber composition to metal |
| FR1571605A (en) * | 1968-03-20 | 1969-06-20 | ||
| US3903026A (en) * | 1972-12-21 | 1975-09-02 | Bridgestone Tire Co Ltd | Rubber composition for adhering zinc or zinc alloy plated steel |
-
1979
- 1979-05-12 DE DE19792919276 patent/DE2919276C2/en not_active Expired
-
1980
- 1980-05-09 FR FR8010475A patent/FR2456609B1/en not_active Expired
- 1980-05-12 JP JP6184380A patent/JPS55156042A/en active Pending
- 1980-05-12 CA CA000351750A patent/CA1168395A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| FR2456609A1 (en) | 1980-12-12 |
| FR2456609B1 (en) | 1985-07-12 |
| DE2919276C2 (en) | 1985-02-21 |
| DE2919276A1 (en) | 1980-11-20 |
| JPS55156042A (en) | 1980-12-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |