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Hardener Tipe Aromatic Amine PDF
Hardener Tipe Aromatic Amine PDF
)NmUENCE OF !ROMATIC !MINE (ARDENERS IN THE #URE +INETICS
OF AN %POXY 2ESIN 5SED IN !DVANCED #OMPOSITES
#OMPOSITE STRUCTURES FOR AEROSPACE APPLICATIONS ARE MAINLY MADE BY THE WELL
KNOWN PREPREG TECHNOLOGY )N
ORDER TO ACHIEVE ADEQUATE PREPREG PROCESSING SCHEDULES AND CONSEQUENTLY MAXIMUM lBER STRENGTH UTILIZATION ONE
HAS TO KNOW IN DEEP THE CURE KINETICS OF MATRIX WHICH HELD THE lBERS TOGETHER 4HIS WORK DESCRIBES A PROCEDURE TO
STUDY THE CURE KINETIC AND HAS AS EXAMPLE HOW AROMATIC AMINE HARDENERS INmUENCE THE CURE KINETICS OF AN EPOXY
RESIN USED IN ADVANCED COMPOSITES 4HE INVESTIGATION WAS CARRIED OUT BY USING THE $3# TECHNIQUE AND IT WAS FOUND
THAT DEPENDING ON THE SYSTEM USED THE CURE KINETICS OF THE FORMULATION OBEYS ORDER N OR AUTOCATALYTIC ORDER
)NTRODUCTION
3TRUCTURAL COMPOSITES ARE ENGINEERING MATERIALS MADE OF ORI
WHERE V IS THE VELOCITY OF REACTION A IS THE REACTION RATE OR CONVERSION RATE
ENTED REINFORCING lBERS DISPERSED IN A METALLIC CERAMIC OR POLYMER IN A GIVEN TIME T "Y A LINEAR PLOTTING %QUATION IT IS POSSIBLE TO KNOW THE
MATRIX 4HE USE OF COMPOSITES MOVED FORWARD IN COMPONENTS OF VALUES OF N AND K
AIRCRAFTS AND SPACE STRUCTURES DUE MAINLY TO PROJECT mEXIBILITY EASY #ONVERSELY THE AUTOCATALYTIC MODEL CONSIDERS INDEPENDENT REAC
PROCESSING LOWER DENSITY ^ GCM
AS WELL AS HIGH MECHANICAL TION ORDERS M AND N AS SHOWN IN %QUATION
STRENGTH AND MODULUS 4HAT MATCHER THE REQUIREMENTS OF THE STRUCTURES
DURING SERVICE 4HIS TURNS THE COMPOSITES PARTICULARLY ATTRACTIVE AS
SUBSTITUTES OF THE METALLIC ALLOYS FOR HIGH DEMANDING AERONAUTICAL
AND SPACE APPLICATIONS
4HE PARAMETERS DADT AND A ARE OBTAINED FROM $3# ISOTHERMS
4HIS WORK FOCUSES ON POLYMER COMPOSITES WHICH ARE MATERIALS
4HE REACTION RATE IS OBTAINED BY THE REACTION HEAT RATIO D(D4 AT A
MADE OF REINFORCING lBERS IN AN EMBEDDED POLYMER MATRIX (OW
TEMPERAT URE 4 FROM THE TOTAL ENTHALPY $( EQUATION
EVER THE PROPERTIES OF COMPOSITES DEPEND ON OTHER FACTORS SUCH
AS THE MOULDING TECHNIQUES AND CURE CYCLES !S A CONSEQUENCE IT
IS VERY IMPORTANT THAT THE VALUES OF THE PROPERTIES USED DURING THE
DESIGN PHASE OF A CERTAIN COMPONENT CONSIDER THE PROCESS VARIABLES
IN ORDER TO OBTAIN PRODUCTS OF HIGH QUALITY AND REQUIRED MECHANICAL WHERE $( IS THE EXPERIMENTAL ENTHALPY CORRESPONDING TO THE TOTAL AREA UP TO
STRENGTH THE REACTION PEAK OR FROM THE THEORETICAL ENTHALPY FOUND IN THE LITERATURE
4HUS IT IS FUNDAMENTAL TO KNOW ALL THE PARAMETERS INVOLVED 4HE VALUE OF A IS DETERMINED BY MEASURING THE PARTIAL REACTION
IN THE CURE CYCLE &OR THAT ONE OF THE MOST USED TECHNIQUES IN THE HEAT AT A TIME T $(P DIVIDED BY THE TOTAL REACTION HEAT IS TAKEN FROM
STUDY OF THE KINETICS OF POLYMERIZATION IS THE DIFFERENTIAL SCANNING THE ISOTHERMAL REACTION $(ISO %QUATION
CALORIMETRY $3# 4HE UNDERSTANDING OF THE CURE KINETICS THAT WILL
DELINEATE THE CURE CYCLE TO BE USED IN THE PROCESSING OF PREPREGS IS OF
FUNDAMENTAL IMPORTANCE FOR GOOD QUALITY ADVANCED COMPOSITES 4HE
CURE KINETICS CAN BE FOLLOWED BY USING TWO $3# METHODS DYNAMIC
AND ISOTHERMAL &INALLY WITH A MINIMUM OF THREE ISOTHERMS ONE CAN OBTAIN THE
4HE ISOTHERMAL METHOD CAN IDENTIFY TWO TYPES OF REACTION N ORDER KINETIC PARAMETERS % ACTIVATION ENERGY AND ! PRE
EXPONENTIAL FAC
OR AUTOCATALYTIC ORDER )F THE MAXIMUM PEAK OF THE ISOTHERM IS CLOSE TOR FROM !RRHENIUS PLOTS
TO T THE SYSTEM OBEYS KINETICS OF N ORDER AND IT CAN BE STUDIED %XCELLENT REVIEWS CONCERNING MECHANISMS AND KINETICS OF THER
EITHER BY DYNAMIC OR ISOTHERMAL METHODS
)N THE CASE WHEN THE MOSET CURE ARE PRESENTED IN LITERATURE
$ESPITE THE CONSIDERABLE
MAXIMUM PEAK IS FORMED IN BETWEEN AND OF THE TOTAL TIME CURRENT RESEARCH EFFORT IN THE lELD OF EPOXY RESIN CURE NUMEROUS ISSUES
OF THE ANALYSIS THE CURE IS AUTOCATALYTIC AND IT SHOULD BE STUDIED HAVE YET TO BE ADDRESSED 4HERE IS A NUMBER OF PARTIALLY CONmICTING
EXCLUSIVELY BY ISOTHERMAL METHOD
EXPLANATIONS PROPOSED IN RECENT YEARS FOR THE REACTION MECHANISMS OF
4HE N ORDER MODEL ASSUMES THAT THE REACTION OBEYS THE %QUA
EPOXY SYSTEM CURE
4HIS WORK DESCRIBES A PROCEDURE TO STUDY THE
TION CURE KINETIC OF POLYMERIC SYSTEMS AND HAS AS EXAMPLE HOW AROMATIC
AMINE HARDENERS INmUENCE THE CURE KINETICS OF AN EPOXY RESIN USED
IN ADVANCED COMPOSITES
E
MAIL MIRABEL IAECTABR
&RVWDHWDO 0DWHULDOV5HVHDUFK
TION ORDER FROM THE $'%"!$$- FORMULATION )T IS OBSERVED THAT )T IS OBSERVED FROM THE RESULTS OF 4ABLE THAT THE VALUE OF ISO
THE MAXIMUM HEAT EVOLUTION THE MAXIMUM REACTION RATE DADT THERMAL $( INCREASES IN MODULE AS ISOTHERMAL CURE TEMPERATURE
OCCURS IN BETWEEN AND OF THE TOTAL REACTION TIME IE AT A GOES HIGHER 4HE INCREASE ON ISOTHERMAL REACTION TEMPERATURE FOR
CONVERSION A x 4HEREFORE THE $'%"!$$- SYSTEM OBEYS THE EXOTHERMIC REACTIONS GENERATES HEAT IN A HIGHER PROPORTION THAN THE
AUTOCATALYTIC CURE KINETICS HEAT GENERATED ON THE REACTION ITSELF
!UTOCATALYTIC CURE KINETICS IMPLIES THAT THE FORMULATION OBEYS )T IS ALSO VERIlED THAT THE !RRHENIUS CONSTANT RATE K AND THE
%QUATION 4HE CONSTANT M IS RELATED TO THE AUTOCATALYTIC CONCENTRA
REACTION ORDER N INCREASES AS REACTION TEMPERATURE GOES HIGHER 4HE
TION OF THE REACTION IE THE CONCENTRATION OF HYDROXYLS GROUPS THAT ARE INCREASE IN REACTION TEMPERATURE CAUSES A DISTINCT DISTRIBUTION OF
BEING GENERATED AS CURE PROCEEDS AND THE CONSTANT N IS RELATED TO THE MOLECULE SPEEDS AND ENERGIES FOLLOWED BY AN INCREASE IN THE AVER
CONSUMPTION OF EPOXY GROUPS "ESIDES M INmUENCES THE INITIAL RATE AGE VALUE OF ENERGY FROM REACTANT MOLECULES !S A CONSEQUENCE A
OF REACTION AND CONTROLS THE SYMMETRY OF THE CURVE AND THE CONSTANT LARGER NUMBER OF MOLECULES HAVE ENOUGH ENERGY THROUGH COLLISION
N DElNES THE REACTION TYPE IE BY THE SHAPE OF THE CURVE 4HUS THE TO SURPASS THE ACTIVATION BARRIER AND CONSEQUENTLY THE REACTION RATE
TOTAL REACTION ORDER M N IS OBVIOUSLY HIGHER THAN ORDER N REACTION MAY INCREASE
KINETICS 4HIS MEANS THAT FORMULATIONS HAVING REACTION KINETICS OF 4HE RESULTS FROM ISOTHERMAL RUNS ALLOW OBTAINING THE VALUES OF
ORDER N AND ORDER M N MUST BE TREATED DIFFERENTLY WHEN CURE CYCLES THE REACTION RATES AND THE CONVERSION &IGURE SHOWS THE REACTION
FOR OPTIMUM COMPOSITE PROCESSING SCHEDULES ARE REQUIRED RATE FROM EACH ISOTHERM REACTION TEMPERATURE THAT WAS OBTAINED AS
FUNCTION OF THE REACTION TIME FOR $'%"!$$3 SYSTEM 4HERE IS A
/RDER N CURE KINETICS MAXIMUM OF REACTION RATE FOR EACH ISOTHERM REACTION TEMPERATURE
&IGURE PRESENTS THE REACTION RATE DADT AS A FUNCTION OF CONVER
$ATA FROM 4ABLE AND RESULTS TAKEN FROM THE ISOTHERMS OF THE
SION A WHERE IT IS CLEAR A MAXIMUM AT ^ CONVERSION FOR ALL
FORMULATION $'%"!$$3 SYSTEM ALLOWS CALCULATION OF THE KINETIC
ISOTHERMAL REACTION TEMPERATURES 4HIS MAXIMUM CONVERTION FOR THE
PARAMETERS THAT ARE PRESENTED IN 4ABLE 4HESE KINETIC PARAMETERS
ISOTHERMS IS RELATED TO THE MECHANISMS FOR BOTH REACTION ORDER N AND
WERE OBTAINED BY USING THE h)SOTHERMAL KINETICSv SOFTWARE
FOR THE AUTOCATALYTIC REACTION ORDER 4HEREFORE FOR $'%"!$$3
SYSTEM THE PLOTS FROM &IGURES AND CONlRM THE REACTION ORDER N
PREVIOUSLY FOUND
0LOTS FROM &IGURES AND SHOW ALSO THAT IN GENERAL THE DADT
VALUE REACHES A MAXIMUM AT A DElNITE TIME ANDOR DElNITE CONVERSION
)N THE PLOT OF &IGURE IT IS VERIlED THAT TEMPERATURE HAS A PRONOUNCED
INmUENCE ON THE REACTION RATE !T LOWER TEMPERATURES ^ # THE
CURVE HAS A SMALLER SLOPE THAN AT HIGHER TEMPERATURES AND THE REAC
&IGURE 4YPICAL CURE ISOTHERMS AT # SHOWING N ORDER REACTION MECHA
NISM FOR THE SYSTEM $'%"!$$3
&IGURE )SOTHERMAL REACTION RATE AS A FUNCTION OF REACTION TIME AT #
# # AND # FOR THE SYSTEM $'%"!$$3
TION TAKES MORE TIME TO REACH THE MAXIMUM CONVERSION RATE DADT AUTOCATALYTIC EFFECT OF M &IGURE ILLUSTRATES THE VARIATION OF M AND
!T HIGHER TEMPERATURES ^
# THE CURVE BECOMES STEEPER N WITH THE TEMPERATURE
IN THE BEGINNING OF THE REACTION AND REACHES THE MAXIMUM REACTION )T CAN BE VERIlED IN &IGURE THAT AT # THE KINETIC EXPONENTS
RATE 4HEREFORE AT THE BEGINING OF COMPOSITE PROCESSING SMALLER M AND N HAVE THE SAME VALUE M N 4HIS MEANS THAT AT THE
TEMPERATURES ARE DESIRABLE ONCE THEY HELP AN ADEQUATE PREPREG HAN
EARLY BEGINNING OF THE POLYMERIZATION REACTION THE AUTOCATALYTIC EFFECT
DLING MOULDING AND CURE CONTROL 4HIS AVOIDS UNDESIRABLE FAST
UN
IS THE SAME AS THE THERMAL EFFECT /N THE OTHER HAND THE VALUE OF M
CONTROLLED REACTIONS WHICH CAN COMPROMISE QUALITY AND PROPERTIES DECREASES AS CURE TEMPERATURE INCREASES APPROACHING ZERO WHEN THE
OF THE PRODUCT TEMPERATURE REACHES NEARLY # )T SHOULD BE NOTED THAT A VALUE
&IGURE CONlRMS THE OBSERVATIONS TAKEN FROM &IGURE 4HE NEARLY CONSTANT FOR THE TOTAL REACTION ORDER M N IS OBTAINED
$'%"!$$3 SYSTEM HAS MAXIMUM CONVERSION AROUND !C
THROUGHOUT THE POLYMERIZATION REACTION WITH N CORRESPONDING TO
CORDING TO %QUATION WHEN CONVERSION A IS EQUAL TO ZERO THE K NEARLY AND M TO OF THE TOTAL REACTION ORDER
REACTION RATE CONSTANT VALUE CAN BE FOUND FROM PLOTS OF DADT AS A 4HE ISOTHERMAL REACTION RATE AS FUNCTION OF TIME OBTAINED FOR THE
FUNCTION OF TIME OR AS FUNCTION OF CONVERSION IE $'%"!$$- AUTOCATALYTIC SYSTEM IS SHOWN IN &IGURES AND 4HE
CONVERSION A IS ALSO SHOWN %ACH CURE ISOTHERM HAS A MAXIMUM AT
>LIA WKXVGAGW N@ THE DADT PARAMETER WHICH IS TYPICAL FOR AN AUTOCATALYTIC MECHANISM
OF N ORDER )N THIS CASE THE CURVES ARE MORE DElNED THAT THE ONES
(OWEVER FROM CHEMISTRY POINT OF VIEW SUCH CONSIDERATION IS NOT SHOWN IN &IGURES AND ACCORDING TO PREVIOUS RESULTS PRESENTED
VALID SINCE THERE IS NO REACTION AT A ZERO CONVERSION AND THEREFORE BY 3EFERIS
THERE IS NO REACTION RATE CONSTANT #OMPARING THESE DATA WITH THE K &IGURES AND ALSO SHOW THE INmUENCE OF THE TEMPERATURE ON THE
VALUES FROM 4ABLE IT IS VERIlED THAT BOTH ARE OF THE SAME ORDER OF REACTION RATE 4HE CURVE OBTAINED AT THE LOWEST TEMPERATURE #
MAGNITUDE PRESENTS THE LOWEST SLOPE AND THE REACTION TAKES LONGER TO REACH THE
&IGURE SHOWS THE !RRHENIUS PLOT LN K VS 4 FOR $'%"!$$3 MAXIMUM CONVERSION RATE DADT !S TEMPERATURE INCREASES ^
FORMULATION 4HE CURVE REPRESENTS THE ACTIVATION ENERGY AND THE VALUE # THE CURVES BECOME STEEPER REACHING THE MAXIMUM REACTION
FOUND IS K*MOL
!CCORDING TO THE LITERATURE CHEMICAL REACTIONS RATE IN A SHORT TIME 4HEREFORE IN ORDER TO GET A TIGHT CONTROL OF THE
HAVE ACTIVATION ENERGIES IN BETWEEN AND K*MOL
4HE ACTI
POLYMERIZATION REACTION DURING COMPOSITE PROCESSING IT IS ADVISABLE
VATION ENERGY OF VERY VISCOUS SYSTEMS IS SMALLER
K*MOL
TO USE LOWER TEMPERATURES IN THE BEGINNING OF THE CURE CYCLE 4HIS
4HEREFORE THE VALUE OF ACTIVATION ENERGY FOR $'%"!$$3 SYSTEM PREVENTS UNCONTROLLED REACTIONS WHICH COULD LEAD TO A COMPOSITE
AGREED WITH THE VALUES FOUND IN LITERATURE
HAVING POOR MECHANICAL PROPERTIES
4HE MAXIMUM REACTION RATE OCCURS AT NEARLY OF CONVER
-ECHANISM OF !UTOCATALYTIC #URE SION &IGURE SUGGESTING THAT WHEN THE CURE REACTION REACHES ITS
4ABLE SHOWS RESULTS FOR $'%"!$$- FORMULATION OBTAINED BY
ISOTHERMAL REACTION RUNS 4HE DATA WERE CALCULATED BY THE h)SOTHERMAL 7DEOH5HVXOWVRIHQWKDOS\RIWKHLVRWKHUPV$+LVRDQGNLQHWLFSDUDPHWHUV
KINETICSv SOFTWARE NQDQGPRIWKH'*(%$''0V\VWHP
)T IS OBSERVED THAT AS FOR THE $'%"!$$- SYSTEM THE ISO
7& $+LVR K4 N M
THERMAL $( THE RATE CONSTANT AND THE KINETIC EXPONENT N INCREASE
-J
PROPORTIONALLY AS A FUNCTION OF TEMPERATURE 4HEN A HIGHER NUMBER OF
MOLECULES ACQUIRES ENOUGH ENERGY FOR COLLISION REACHING THE REACTION
ACTIVATION BARRIER AND CONSEQUENTLY INCREASING THE REACTION RATE
/N THE OTHER HAND THE KINETIC EXPONENT M DECREASES AS TEMPERATURE
INCREASE DUE TO THE EFFECT OF THE THERMAL CATALYSIS SUPERSEDING THE
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# # AND # FOR THE SYSTEM $'%"!$$3 $'%"!$$3 SYSTEMS
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