CA1205700A - Secondary matrix reinforcement using carbon microfibers and method for making carbon microfibers - Google Patents
Secondary matrix reinforcement using carbon microfibers and method for making carbon microfibersInfo
- Publication number
- CA1205700A CA1205700A CA000435320A CA435320A CA1205700A CA 1205700 A CA1205700 A CA 1205700A CA 000435320 A CA000435320 A CA 000435320A CA 435320 A CA435320 A CA 435320A CA 1205700 A CA1205700 A CA 1205700A
- Authority
- CA
- Canada
- Prior art keywords
- fibers
- microfibers
- carbon
- carbon microfibers
- continuous
- 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
-
- 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
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/08—Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
- B29C70/081—Combinations of fibres of continuous or substantial length and short fibres
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/903—Microfiber, less than 100 micron diameter
-
- 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
- Y10T428/30—Self-sustaining carbon mass or layer with impregnant or other layer
Abstract
Abstract:
SECONDARY MATRIX REINFORCEMENT USING CARBON
MICROFIBERS AND METHOD FOR MAKING CARBON MICROFIBERS
A continuous fiber composite having carbon micro-fibers dispersed in the resin filling the interstices between the continuous fibers to enhance the transverse properties of the composite. The carbon microfibers are made by soaking carbon fibers in an intercalating acid solution comprising a mixture of fuming nitric and sulfuric acid to weaken the intercrystallite bonds.
Gentle stirring of solution separates the carbon microfibers from the host fibers. The microfibers are then separated from the intercalating acid solution and washed to remove the residual acid.
SECONDARY MATRIX REINFORCEMENT USING CARBON
MICROFIBERS AND METHOD FOR MAKING CARBON MICROFIBERS
A continuous fiber composite having carbon micro-fibers dispersed in the resin filling the interstices between the continuous fibers to enhance the transverse properties of the composite. The carbon microfibers are made by soaking carbon fibers in an intercalating acid solution comprising a mixture of fuming nitric and sulfuric acid to weaken the intercrystallite bonds.
Gentle stirring of solution separates the carbon microfibers from the host fibers. The microfibers are then separated from the intercalating acid solution and washed to remove the residual acid.
Description
~)57~
SECONDARY MATRIX REIN _R EMFNT_USING CAR~ON
MICROFIBERS AND METHOD FOR MAKING CAR ON MICROFIBERS
Backqround of th _ _nvention Field of the Invention The invention is related to the field of fibrous composite materials and in particular to a method for making carbon microfibers for secondary matrix reinforce-5ment of fibrous composites.
Prior Art The use of fiber reinforced composite materials in 10the place of metals and ceramics has been rapidly increasing. Carbon fiber reinforced composites are currently receiving considerable attention because of their high strength to weight ratio, temperature resistance, corrosion resistance, impact strength, and 15other desirable properties. Workers in the field have been continuously working to improve the strength of the carbon fiber reinforced composites. The thrust of their efforts has been along two distinct pa~hs. One has been to improve the strength and flexibility of the carbon 20fibers themselves as disclosed by Schulz in U.S. patents 4,138,525 and 4,014,725. The other has been direc~ed to surface treating the fibers to improve the adhesion between the fibers and the resins. Typical of this latter thrust ar~ the methods disclosed by Lind et al in 25U.S. patent 4,269,876, Kalnin in U.S. patent 4,073,869, Joo et al in U.S. patent 3,989,802 and others.
The physical properties of fiber reinforced com-posites along the fiber direction are quite good and satisfact~ry ~or many applications. In contrast however 30the physical properties of the fiber reinforced composites transverse to the fiber direction is relatively low when compared to those along the fiber .,",. ' ~
450-82-Ol~
~ 2~ 7~D
direction. This is because ~he transverse behavior is matrix dominated. This deficiency may be partially rectified by fiber reinforcing the neat resin between the primary reinforcing fibers with transverse discontinuous fibers. This requires microfiber small enouyh to fit into the interstices between the primary fibers. Commercially available microfibers, such as Wollastonite or silicon carbide whiskers approach the desired size range. Wollastonite is a low cost mineral fiber with limited physical properties. In contrast silicon carbide whiskers have good physical properties but are very expensive. Therefore neither Wollastonite nor silicon carbide are well suited to interstitial reinforcement of continuous fiber composites. The Wollastonite fibers are relatively large and the aspect ratio of the silicon carbide whiskers is not suEficiently uniform.
The present invention describes a method for making carbon micro~ibers that have aspect ratios in the desired range and diameters sufficiently small to be ~sed for the interstitial reinforcement of continuous fiber composites.
Summary of the Inv ntion The invention is a reinforced composite of the type having a continuous fiber matrix impregnated with a resin filling the interstices having improved transverse properties. The improvement in the transverse properties is obtained by a plurality of carbon microfibers randomly dispersed in the resin. The carbon microfibers have a cross section significantly smaller than the cross section of the continuous fibers o~ the !~
~r~
fiber matrix. The carbon microfibers being small enough to be randomly dispersed in the interstices of the continuous fiber matrix.
One aclvantage of the invention is that the carbon microfibers dispersed in the interstices of the continuous fiber matrix significantly increase the transverse properties of the composite. Another advantage of the invention is that the composite can be made using conventional composite materials fabrication methods. Yet another advantage is that the microfibers may be made from scrap or chopped carbon fibers.
These and other advantages of the invention will become apparent from a reading of the following detailed description of the invention and the method for making the carbon microfibers.
Brief Description of the Drawings FIGURE 1 i s a microphotograph showing the onset of the fiber breakup after being immersed in the intercalating acid solution for 30 minutes.
FIGURE 2 is a microphotograph of the intercalating solution after 90 minutes showing the separated microfibers.
FIGURE 3 is a photograph taken wi~h a scanning elec-tron microscope illustrating how the breakup of large carbon fiber gives rise to the various sizes and shapes of the microfibers produced by the disclosed method.
Deta1led Descrl~ _on of the Invention Commercially available carbon fiber is typically about 8 microns in diameter. In this respect, carbon fibers are not unlike other reinforcing fibers used in composite materials. However, unlike most other rein-forcing fibers, such as glass, carbon fiber possesses a complex internal structure that contributes to its out-standing physical properties in the direction parallel to the fiber axis.
This structure has been elucidated by numerous workers in the field. ~ comprehensive review of the car-bon fiber structure is presented by Reynolds in Chemist_~
and Ph sics of Carbon, Volume II, Dekker New York 1973.
Y . ___ Briefly, the carbon fiber structure consists of ribbon or fibrillar crystallites that twist, intertwine, and un-dulate along the longitudinal axis of the fiber. The substructure of the ribbon or fibrillar crystallites is composed of aligned graphitic planes. These crystallites may only be a few planes in thickness, but extend for hundreds of angstroms along the fiber axis.
High temperature heat treatment of the carbon fibers will improve ~he alignment o~ the fibers, reduce undula-tions o~ the ribbons, and ~ubstantially increase the longitudinal fiber modulus. The degree to which these benefits are obtained depends to a large part upon the heat treatment as disclosed by W. Watts and W~ Johnson in the Proceedings of the 3rd International Conference on Industrial Carbons and Graphite, London 1970, page 417.
The high degree of crystal alignment in ultra-high modulus fibers results in relatively low tensile proper-ties transverse ~o the ~iber axis due to weak Van der-Waals bonding between basal planes and reduced interlocking. Therefore, it is reasonable to expect that such fibers would split along the crystallite boundries _5_ ~2~
into smaller particles having sufficiently high aspect ratios and small diameters to qualify as microfibers.
Moreover, if the crystallites themselves were separated from larger fibers, their physical properties would approach theoretical limits.
In accordance with the above analysis, a method has been developed to produce carbon microfibers small enough to fit into the interstices between the primary fibers of a continuous fiber composite. The method comprises immersing the carbon fibers in a solution of two or more strong intercalating acids ~3 weaken and disrupt the intercrystallite bonding between the aligned graphitic planes. Mechanical agitation of the immersed fibers separates the cryskallites whose inter-crystallite boun-drie~ are weakened by he combina~ion of intercalatingacids from the immersed fibers. The residue oE the carbon fibers is removed from the solution then the acid solution is diluted with water. The carbon microfibers are then separated from the diluted solution by filtering. Repeated washing and filtering steps are used to remove the residual acid from the separated microfibers.
A preferred solution of strong intercalating acid comprises a mixture of 50 to 70 percent fuminy nitric acid and 30 to 50 percent sulfuric acid and in par~icular a mixture containing 60 percent fuming nitric acid and 40 percent sulfuric acid (95% aq.) at a temperature of 85C.
As an example o~ the process, high modulus pitch-based carbon fiber, such as Union Carbide P300 carbon fibers made by Union Carbide Corporation of New York, New York was immersed in a mixture of 60~ fuming nitric acid (HNO3) and 40% sulfuric acid (H25O4, 95~ aq.) at 85~C.
Gentle stirring action was employed to ayitate the fibers and separate the microfibers from the immersed fibers.
After 30 ~inutes a sample of the fibers was extracted and 1,1., j~"
observed under a microscope. As illustrated in FIGURE 1, which is a microphotograph o~ the ~ithdrawn sample taken at 180x magnification, the onset of the fiber breakup is discernible. In particular one of the central fibers has become enlarged and splintering microfibers are clearly visible. With further treatment in the intercalating solution the carbon microfibers separate from the base fibers and float free in the solution as illustrated in FIGURE 2. FIGURE 2 is a microphotograph of the solution taken 90 minutes after the carbon fibers were immersed in the solution of intercalating acids and shows the large quantity of high aspect ratio of carbon microfibers produced. ~ closer inspection of the splintering fibers using a scanning electron microscope is illustrated in 15 FIGURE 3. This photograph was taken at a magnification of 1.31KX and more clearly shows how the various sizes and shapes of microfiber are produced by this method.
These microfibers may be round, irregular or flat ribbons ranging from tenths of a micron to several microns in cross section.
As previously indicated the microfibers may be separated from the solution by filtering. Repeated washings are used to remove the residual intercalating acid solution prior to incorporating them into continuous fiber composites.
One advantage of this method for making carbon microfibers is that they may be produced at relatively low cost using scrap or chopped carbon fibers.
In the fabrication of the continuous fiber composite material the separated carbon microfibers are dispersed in the resin material prior to impreg~ating the continuous fibers. The continous fiber composite is made using the res~n having the dispersed microfibers. As the primary fibers are impregnated with the resin, the carbon microfibers become randomly dispersed in the interstices _7- ~2~
significantly enhancing the transverse properties of the composite.
Although the invention has been described using car-bon fibers and a particular combination of intercalating acids, those skilled in the art will recognize that the disclosed method is equally applicable to other materials and that other intercalating acids may be used to weaken the intercrystallite boundaries within the spirit of the invention as described herein and set forth in the appended claims.
SECONDARY MATRIX REIN _R EMFNT_USING CAR~ON
MICROFIBERS AND METHOD FOR MAKING CAR ON MICROFIBERS
Backqround of th _ _nvention Field of the Invention The invention is related to the field of fibrous composite materials and in particular to a method for making carbon microfibers for secondary matrix reinforce-5ment of fibrous composites.
Prior Art The use of fiber reinforced composite materials in 10the place of metals and ceramics has been rapidly increasing. Carbon fiber reinforced composites are currently receiving considerable attention because of their high strength to weight ratio, temperature resistance, corrosion resistance, impact strength, and 15other desirable properties. Workers in the field have been continuously working to improve the strength of the carbon fiber reinforced composites. The thrust of their efforts has been along two distinct pa~hs. One has been to improve the strength and flexibility of the carbon 20fibers themselves as disclosed by Schulz in U.S. patents 4,138,525 and 4,014,725. The other has been direc~ed to surface treating the fibers to improve the adhesion between the fibers and the resins. Typical of this latter thrust ar~ the methods disclosed by Lind et al in 25U.S. patent 4,269,876, Kalnin in U.S. patent 4,073,869, Joo et al in U.S. patent 3,989,802 and others.
The physical properties of fiber reinforced com-posites along the fiber direction are quite good and satisfact~ry ~or many applications. In contrast however 30the physical properties of the fiber reinforced composites transverse to the fiber direction is relatively low when compared to those along the fiber .,",. ' ~
450-82-Ol~
~ 2~ 7~D
direction. This is because ~he transverse behavior is matrix dominated. This deficiency may be partially rectified by fiber reinforcing the neat resin between the primary reinforcing fibers with transverse discontinuous fibers. This requires microfiber small enouyh to fit into the interstices between the primary fibers. Commercially available microfibers, such as Wollastonite or silicon carbide whiskers approach the desired size range. Wollastonite is a low cost mineral fiber with limited physical properties. In contrast silicon carbide whiskers have good physical properties but are very expensive. Therefore neither Wollastonite nor silicon carbide are well suited to interstitial reinforcement of continuous fiber composites. The Wollastonite fibers are relatively large and the aspect ratio of the silicon carbide whiskers is not suEficiently uniform.
The present invention describes a method for making carbon micro~ibers that have aspect ratios in the desired range and diameters sufficiently small to be ~sed for the interstitial reinforcement of continuous fiber composites.
Summary of the Inv ntion The invention is a reinforced composite of the type having a continuous fiber matrix impregnated with a resin filling the interstices having improved transverse properties. The improvement in the transverse properties is obtained by a plurality of carbon microfibers randomly dispersed in the resin. The carbon microfibers have a cross section significantly smaller than the cross section of the continuous fibers o~ the !~
~r~
fiber matrix. The carbon microfibers being small enough to be randomly dispersed in the interstices of the continuous fiber matrix.
One aclvantage of the invention is that the carbon microfibers dispersed in the interstices of the continuous fiber matrix significantly increase the transverse properties of the composite. Another advantage of the invention is that the composite can be made using conventional composite materials fabrication methods. Yet another advantage is that the microfibers may be made from scrap or chopped carbon fibers.
These and other advantages of the invention will become apparent from a reading of the following detailed description of the invention and the method for making the carbon microfibers.
Brief Description of the Drawings FIGURE 1 i s a microphotograph showing the onset of the fiber breakup after being immersed in the intercalating acid solution for 30 minutes.
FIGURE 2 is a microphotograph of the intercalating solution after 90 minutes showing the separated microfibers.
FIGURE 3 is a photograph taken wi~h a scanning elec-tron microscope illustrating how the breakup of large carbon fiber gives rise to the various sizes and shapes of the microfibers produced by the disclosed method.
Deta1led Descrl~ _on of the Invention Commercially available carbon fiber is typically about 8 microns in diameter. In this respect, carbon fibers are not unlike other reinforcing fibers used in composite materials. However, unlike most other rein-forcing fibers, such as glass, carbon fiber possesses a complex internal structure that contributes to its out-standing physical properties in the direction parallel to the fiber axis.
This structure has been elucidated by numerous workers in the field. ~ comprehensive review of the car-bon fiber structure is presented by Reynolds in Chemist_~
and Ph sics of Carbon, Volume II, Dekker New York 1973.
Y . ___ Briefly, the carbon fiber structure consists of ribbon or fibrillar crystallites that twist, intertwine, and un-dulate along the longitudinal axis of the fiber. The substructure of the ribbon or fibrillar crystallites is composed of aligned graphitic planes. These crystallites may only be a few planes in thickness, but extend for hundreds of angstroms along the fiber axis.
High temperature heat treatment of the carbon fibers will improve ~he alignment o~ the fibers, reduce undula-tions o~ the ribbons, and ~ubstantially increase the longitudinal fiber modulus. The degree to which these benefits are obtained depends to a large part upon the heat treatment as disclosed by W. Watts and W~ Johnson in the Proceedings of the 3rd International Conference on Industrial Carbons and Graphite, London 1970, page 417.
The high degree of crystal alignment in ultra-high modulus fibers results in relatively low tensile proper-ties transverse ~o the ~iber axis due to weak Van der-Waals bonding between basal planes and reduced interlocking. Therefore, it is reasonable to expect that such fibers would split along the crystallite boundries _5_ ~2~
into smaller particles having sufficiently high aspect ratios and small diameters to qualify as microfibers.
Moreover, if the crystallites themselves were separated from larger fibers, their physical properties would approach theoretical limits.
In accordance with the above analysis, a method has been developed to produce carbon microfibers small enough to fit into the interstices between the primary fibers of a continuous fiber composite. The method comprises immersing the carbon fibers in a solution of two or more strong intercalating acids ~3 weaken and disrupt the intercrystallite bonding between the aligned graphitic planes. Mechanical agitation of the immersed fibers separates the cryskallites whose inter-crystallite boun-drie~ are weakened by he combina~ion of intercalatingacids from the immersed fibers. The residue oE the carbon fibers is removed from the solution then the acid solution is diluted with water. The carbon microfibers are then separated from the diluted solution by filtering. Repeated washing and filtering steps are used to remove the residual acid from the separated microfibers.
A preferred solution of strong intercalating acid comprises a mixture of 50 to 70 percent fuminy nitric acid and 30 to 50 percent sulfuric acid and in par~icular a mixture containing 60 percent fuming nitric acid and 40 percent sulfuric acid (95% aq.) at a temperature of 85C.
As an example o~ the process, high modulus pitch-based carbon fiber, such as Union Carbide P300 carbon fibers made by Union Carbide Corporation of New York, New York was immersed in a mixture of 60~ fuming nitric acid (HNO3) and 40% sulfuric acid (H25O4, 95~ aq.) at 85~C.
Gentle stirring action was employed to ayitate the fibers and separate the microfibers from the immersed fibers.
After 30 ~inutes a sample of the fibers was extracted and 1,1., j~"
observed under a microscope. As illustrated in FIGURE 1, which is a microphotograph o~ the ~ithdrawn sample taken at 180x magnification, the onset of the fiber breakup is discernible. In particular one of the central fibers has become enlarged and splintering microfibers are clearly visible. With further treatment in the intercalating solution the carbon microfibers separate from the base fibers and float free in the solution as illustrated in FIGURE 2. FIGURE 2 is a microphotograph of the solution taken 90 minutes after the carbon fibers were immersed in the solution of intercalating acids and shows the large quantity of high aspect ratio of carbon microfibers produced. ~ closer inspection of the splintering fibers using a scanning electron microscope is illustrated in 15 FIGURE 3. This photograph was taken at a magnification of 1.31KX and more clearly shows how the various sizes and shapes of microfiber are produced by this method.
These microfibers may be round, irregular or flat ribbons ranging from tenths of a micron to several microns in cross section.
As previously indicated the microfibers may be separated from the solution by filtering. Repeated washings are used to remove the residual intercalating acid solution prior to incorporating them into continuous fiber composites.
One advantage of this method for making carbon microfibers is that they may be produced at relatively low cost using scrap or chopped carbon fibers.
In the fabrication of the continuous fiber composite material the separated carbon microfibers are dispersed in the resin material prior to impreg~ating the continuous fibers. The continous fiber composite is made using the res~n having the dispersed microfibers. As the primary fibers are impregnated with the resin, the carbon microfibers become randomly dispersed in the interstices _7- ~2~
significantly enhancing the transverse properties of the composite.
Although the invention has been described using car-bon fibers and a particular combination of intercalating acids, those skilled in the art will recognize that the disclosed method is equally applicable to other materials and that other intercalating acids may be used to weaken the intercrystallite boundaries within the spirit of the invention as described herein and set forth in the appended claims.
Claims (2)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. In a continuous fiber composite material comprising a continuous fiber matrix impregnated with a resin filling the interstices, the improvement comprising a plurality of carbon microfibers randomly dispersed in the resin, said carbon microfibers having a cross section significantly smaller than the cross section of the fibers in said continuous fiber matrix.
2. A composite comprising a matrix of continuous fibers, said continuous;
fibers having a predetermined cross section;
a resin impregnating said matrix of continuous fibers and filling the interstices between said continuous fibers; and a plurality of carbon microfibers dispersed in said resin and randomly disposed in said interstices, said carbon microfibers having a cross section substantially smaller than the cross section of said continuous microfibers.
fibers having a predetermined cross section;
a resin impregnating said matrix of continuous fibers and filling the interstices between said continuous fibers; and a plurality of carbon microfibers dispersed in said resin and randomly disposed in said interstices, said carbon microfibers having a cross section substantially smaller than the cross section of said continuous microfibers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/432,216 US4472541A (en) | 1982-10-01 | 1982-10-01 | Secondary matrix reinforcement using carbon microfibers |
| US432,216 | 1982-10-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1205700A true CA1205700A (en) | 1986-06-10 |
Family
ID=23715232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000435320A Expired CA1205700A (en) | 1982-10-01 | 1983-08-25 | Secondary matrix reinforcement using carbon microfibers and method for making carbon microfibers |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4472541A (en) |
| EP (1) | EP0105809A2 (en) |
| JP (1) | JPS5981339A (en) |
| CA (1) | CA1205700A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4565727A (en) * | 1983-09-12 | 1986-01-21 | American Cyanamid Co. | Non-woven activated carbon fabric |
| FR2589473B1 (en) * | 1985-10-30 | 1988-09-16 | Saint Gobain Vetrotex | POLYMERIZABLE RESIN COMPOSITION REINFORCED BY CUT WIRES |
| US4681801A (en) * | 1986-08-22 | 1987-07-21 | Minnesota Mining And Manufacturing Company | Durable melt-blown fibrous sheet material |
| US4842924A (en) * | 1986-08-25 | 1989-06-27 | Farris Richard J | Novel compositions based on reinforcement with microfibrillar networks of rigid-rod polymers |
| US5102601A (en) * | 1986-08-25 | 1992-04-07 | Farris Richard J | Process for fabricating novel compostes based on reinforcement with microfibrillar networks of rigid-rod polymers |
| WO1992002577A1 (en) * | 1990-07-30 | 1992-02-20 | Hyperion Catalysis International | Adhesive compounds |
| US5763042A (en) * | 1994-06-28 | 1998-06-09 | Reichhold Chemicals, Inc. | Reinforcing structural rebar and method of making the same |
| US5876553A (en) * | 1994-06-28 | 1999-03-02 | Marshall Industries Composites, Inc. | Apparatus for forming reinforcing structural rebar |
| CA2267075C (en) | 1996-10-07 | 2004-05-18 | Mark A. Kaiser | Reinforced composite product and apparatus and method for producing same |
| FI103740B (en) * | 1998-06-02 | 1999-08-31 | Valmet Corp | Nipple roll diaper |
| US20050113771A1 (en) * | 2003-11-26 | 2005-05-26 | Kimberly-Clark Worldwide, Inc. | Odor control in personal care products |
| US20050142966A1 (en) * | 2003-12-31 | 2005-06-30 | Kimberly-Clark Worldwide, Inc. | Odor control materials and face masks including odor control materials |
| US7655829B2 (en) | 2005-07-29 | 2010-02-02 | Kimberly-Clark Worldwide, Inc. | Absorbent pad with activated carbon ink for odor control |
| US9352267B2 (en) | 2012-06-20 | 2016-05-31 | Hollingsworth & Vose Company | Absorbent and/or adsorptive filter media |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3016599A (en) * | 1954-06-01 | 1962-01-16 | Du Pont | Microfiber and staple fiber batt |
| US3382305A (en) * | 1954-10-29 | 1968-05-07 | Du Pont | Process for preparing oriented microfibers |
| US2957756A (en) * | 1958-03-18 | 1960-10-25 | Union Carbide Corp | Filamentary graphite and method for producing the same |
| GB1257022A (en) * | 1968-01-03 | 1971-12-15 | ||
| US3989802A (en) * | 1970-02-11 | 1976-11-02 | Great Lakes Carbon Corporation | Treatment of carbon fibers |
| US3788935A (en) * | 1970-05-27 | 1974-01-29 | Gen Technologies Corp | High shear-strength fiber-reinforced composite body |
| US3754957A (en) * | 1970-08-20 | 1973-08-28 | Celanese Corp | Enhancement of the surface characteristics of carbon fibers |
| US3791840A (en) * | 1970-10-21 | 1974-02-12 | Union Carbide Corp | Treatment of carbon fibers to improve shear strength in composites |
| US3746560A (en) * | 1971-03-25 | 1973-07-17 | Great Lakes Carbon Corp | Oxidized carbon fibers |
| US3778334A (en) * | 1971-04-20 | 1973-12-11 | Du Pont | High modulus organic fiber layers alternating with inorganic fiber layers in a resin matrix |
| US3853610A (en) * | 1972-03-10 | 1974-12-10 | Dow Chemical Co | Composite materials comprising epoxy resin matrix and carbon fibers |
| US4014725A (en) * | 1975-03-27 | 1977-03-29 | Union Carbide Corporation | Method of making carbon cloth from pitch based fiber |
| US4073869A (en) * | 1975-06-05 | 1978-02-14 | Celanese Corporation | Internal chemical modification of carbon fibers to yield a product of reduced electrical conductivity |
| US4138525A (en) * | 1976-02-11 | 1979-02-06 | Union Carbide Corporation | Highly-handleable pitch-based fibers |
| US4269876A (en) * | 1977-10-04 | 1981-05-26 | Rolls-Royce Limited | Treatment of carbon fibre |
| JPS56164842A (en) * | 1980-05-23 | 1981-12-18 | Toray Industries | Carbon fiber reinforced thermoplastic resin molding |
-
1982
- 1982-10-01 US US06/432,216 patent/US4472541A/en not_active Expired - Fee Related
-
1983
- 1983-08-25 CA CA000435320A patent/CA1205700A/en not_active Expired
- 1983-09-29 JP JP58179503A patent/JPS5981339A/en active Pending
- 1983-09-30 EP EP83401920A patent/EP0105809A2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US4472541A (en) | 1984-09-18 |
| JPS5981339A (en) | 1984-05-11 |
| EP0105809A2 (en) | 1984-04-18 |
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