COMPOSITE POLYMERS

A GUIDE TO FABRICATING COMPOSITES

Table of Contents
SECTION 1
Product Description
Description of HETRON® and AROPOL™ Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

SECTION 2
Initiators, Promoters and Inhibitors
Methyl Ethyl Ketone Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Benzoyl Peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
Cumene Hydroperoxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
t-Butyl Peroxybenzoate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Cobalt Naphthenate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Dimethylaniline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
Copper Naphthenate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Inhibitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
Safety . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

SECTION 3
Thixotropes, Antimony Oxides and Other Additives
Thixotropes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Antimony Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
Alumina Trihydrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Other Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Intumescent Coatings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Ultraviolet Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
Air Release Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Wax Topcoats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Abrasion Resistant Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

SECTION 4
Reinforcements
Standard Reinforcement Sequence . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
Surfacing Veil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
Chopped Strand Mat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Woven Roving . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
Continuous Strand Roving . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

SECTION 5
Resin Preparation
FDA Compliance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Adjusting Promoter/Initiator Levels for Practical Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
Preparing the Resin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
Making a Test Laminate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Post Curing the Laminate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
WITH H E T R O N® A N D A R O P O L™ R E S I N S

SECTION 6
Fabrication Methods
Fabrication Standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Hand Lay-Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Spray-Up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Filament Winding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Pultrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Centrifugal Casting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Resin Transfer Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Linings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Fabricating Thick Sections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
Finishing Processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

SECTION 7
Inspecting a Laminate
Visual Inspection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Barcol Hardness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
Acetone Sensitivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

SECTION 8
Health, Safety and Regulatory Information
Material Safety Data Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Styrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Flammability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Health Concerns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
Eye Contact . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25
Inhalation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25
Ingestion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25
Chronic Health Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .25
Resin Spills . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
Disposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

SECTION 9
Appendices
Appendix A – Promoter and Initiator Addition Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
Appendix B – Ashland Chemical Technical Service Contacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
Appendix C – North American Suppliers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
Appendix D – Equipment Suppliers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
Appendix E – Trouble Shooting Guide for Curing Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
Appendix F – Weight to Volume Conversion Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Appendix G – Visual Acceptance Criteria for Cured Laminates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
COMPOSITE POLYMERS
S E C T I O N 1

Product Description
The development and manufacture of HETRON® and AROPOL™ polyester and vinyl ester
resins have been a continuing process since 1954. They have been used to fabricate thousands of
different types of corrosion resistant FRP equipment. Many versions of HETRON and AROPOL
resins have been developed for ease of handling during hand lay-up, spray-up, filament winding,
pultrusion, centrifugal casting and most other methods of commercial fabrication. Ashland
Specialty Chemical provides a variety of thermoset resins for corrosion resistant applications.
Table 1 summarizes the different types of resins.

* Corrosion Resistant isophthalic based products

** Please contact Ashland Technical Service for more information on MODAR products
P promoted system
T-XX thixed system with a room temperature gel (RTG) of XX minutes using 1.25% of an MEKP initiator

2
 S E C T I O N 1

Table 1

Liquid / Flame Retardance

Fume (based on the
Resin Type Resin Number Fabrication Applications Service Fume ASTM E-84 Tunnel Test) Thixed Promoted F-Cat
Service
Class I Class II
Chlorendic HETRON® 72 High viscosity base resin, bulk molding compound (BMC), X X X – with 5%
Polyester sheet molding compound (SMC), coating formulations antimony
trioxide

HETRON® 92 Pultrusion, BMC, SMC, molded electrical sheet, X X – with 3% X

antimony
vacuum bagging, Mil Specification trioxide

HETRON® 92FR Hand lay-up, spray-up X X X

X X – with 3% X X
HETRON® 92AT Hand lay-up, spray-up antimony
trioxide

HETRON® 197 Hand lay-up, spray-up, press molding, X X – with 5%

pultrusion, vacuum bagging antimony
trioxide

X X – with 5% X
HETRON® Hand lay-up, spray-up, filament winding antimony
197-3 trioxide

HETRON® 197P Hand lay-up, spray-up, filament winding X X – with 5% X X

antimony
trioxide

Bisphenol A HETRON® 700 Hand lay-up, spray-up, filament winding,

Fumarate press molding, pultrusion, coating formulations, X
Polyester FDA applications

X – with 3%
Isophthalic HETRON® 99P Hand lay-up, spray-up, filament winding, X antimony X X X
Polyester fire retardant trioxide
AROPOL™ Hand lay-up, spray-up, filament winding, X X X
7241T-15* series FDA applications

AROPOL™ Hand lay-up, spray-up, filament winding, X X X

7334T-15* series FDA applications
Furan HETRON® 800 Hand lay-up, spray-up, filament winding, X
flake glass coating
Vinyl Ester HETRON® 922 Hand lay-up, spray-up, filament winding, X
flake glass coatings, FDA applications
HETRON® 922L Hand lay-up, spray-up, filament winding, flake glass coatings, X
applications requiring lower viscosity than Hetron 922, FDA applications

HETRON® 942/35 Hand lay-up, spray-up, filament winding, flake glass coatings, X
less than 35% styrene, FDA applications

HETRON® 970/35 Hand lay-up, spray-up, filament winding, flake glass coatings, X
applications requiring maximum solvent resistance, less than 35% styrene
HETRON® 980 Hand lay-up, spray-up, filament winding, flake glass coatings, X
higher temperature resistance than Hetron 922

HETRON® 980/35 Hand lay-up, spray-up, filament winding, flake glass coating, X
less than 35% styrene
X – with 3%
HETRON® FR992 Hand lay-up, spray-up, filament winding,flake glass coatings X antimony
trioxide

HETRON® FR992 Sb Hand lay-up, spray-up, filament winding,flake glass coatings X X

Hand lay-up, spray-up, filament winding, X X
HETRON® FR998/35 flake glass coatings, less than 35% styrene
Miscellaneous
Fire HETRON® Hand lay-up, spray-up, filament winding X X – with 3% X X X
Retardant 604T-20 antimony
trioxide
HETRON® FR620T20 Hand lay-up, spray-up, filament winding X X X X X
HETRON® 625P Hand lay-up, spray-up, filament winding X X X X X
HETRON® Hand lay-up, spray-up, filament winding X X X X X
692TP-25

MODAR® 814a** RTM, hand lay-up, spray lay-up, filament winding X – with ATH X – with ATH

MODAR 816a**
®
RTM, hand lay-up, spray lay-up, filament winding X – with ATH X – with ATH
 COMPOSITE POLYMERS
S E C T I O N 2

Initiators, Promoters and Inhibitors

Initiators, also referred to as catalysts, are organic peroxides that work together with promoters
to initiate the chemical reaction that causes a resin to gel and harden. The amount of time from
which the initiator is added until the resin begins to gel is referred to as the “gel time.” Initiator
and promoter levels can be adjusted, to a certain extent, to shorten or lengthen the gel time and
accommodate both high and low temperatures. For example, Figure 1 shows how the gel time of
a prepromoted resin system shortens with increasing temperature.
If a longer gel time is required, inhibitors can be added to a resin system to lengthen the gel time.
However, care should be taken not to decrease or increase promoter/initiator levels beyond what is
recommended for that particular resin. If the level of initiator is too low, incomplete cure may
occur, which could result in decreased physical properties and chemical resistance. On the other
hand, levels that are too high could cause the laminate, particularly thick laminates, to delaminate,
burn, or discolor during curing. In addition, if promoter or initiator levels are too high, the result
can be undercure. Promoter, initiator and inhibitor levels for specific resins are listed in Appendix A.

INITIATORS1
There are two primary types of initiators recommended for curing HETRON® and AROPOL™
resins at room temperature: methyl ethyl ketone peroxide (MEKP) and benzoyl peroxide (BPO).
A third, less common initiator type is cumene hydroperoxide (CHP) which is often recommended
for blending with MEKP. In other processes, such as pultrusion, different types of initiators are
used. Initiators for the pultrusion process are heat activated and are not used with promoters.
The proper choice of an initiator is critical to achieving expected chemical resistance. Care must be
taken not to select initiators that are too fast or slow in curing. Unusually fast or slow cure times
could result in reduced corrosion resistance in the final cured product.

Methyl Ethyl Ketone Peroxide (MEKP)

Figure 1. Gel Time vs. Temperature MEKP is the most widely used initiator system. MEKP is
80
used with promoters, usually 6% cobalt naphthenate or
6% or 12% cobalt octoate and dimethylaniline (DMA)
70 or diethylaniline (DEA)1. The MEKP used most often is
supplied at 9% active oxygen.
60

Many resin producers require the use of special MEKPs

50
Gel Time (min.)

that contain very low levels of hydrogen peroxide. This is

40 because the vinyl ester resins they produce can foam when
they come in contact with hydrogen peroxide. Ashland’s
30 Flexible-Catalyzation (F-Cat), High Performance epoxy
vinyl ester resins (EVERs) do not foam when catalyzed
20
with standard MEKPs. The use of standard MEKPs
10 allows for much greater control of the exotherm during
cure. Ashland Technical Service should be contacted for
0
65 70 75 80 85
information on alternative initiators for use with HET-
1.00%MEKP Temperature (oF)
RON and AROPOL resins and appropriate exotherm con-
1.25%MEKP trol. See Appendix B for the contact in your area.
1.50%MEKP

Benzoyl Peroxide (BPO)

BPO requires the addition of DMA or DEA for room temperature curing. For curing at elevated
temperatures, greater than 160°F, BPO is used without DMA or DEA. BPO is not as widely used
as MEKP, primarily because it is more difficult to mix into the resin system than MEKP; it may
4
 S E C T I O N 2

cause higher exotherm temperatures, and it is more difficult to fully post cure. However, the
following is an application in which a BPO system is definitely recommended over a MEKP
cure system.
• In sodium hypochlorite environments, improved corrosion resistance is observed with
DMA/BPO cure system. HETRON® FR992 cured with BPO/DMA will turn a bright
yellow when exposed to the sun. This does not effect chemical resistance.
BPO is available as a powder, a paste or an aqueous dispersion. The aqueous dispersion is not
recommended for corrosion applications. Our tests show that aqueous BPO solutions compromise
corrosion resistance in selected environments.The paste form is the most widely used type with
polyesters and vinyl esters. BPO crystals are also available, however they are used less frequently.
The paste is generally supplied in a 50% active form and the crystals in 98% active form. To
achieve the same gel time with paste and crystals, half the amount of crystals should be used as
paste. For example, 2.0 grams of paste will react to give the same gel time as 1.0 gram of the
crystals. BPO crystals are shock sensitive and must be predissolved in styrene prior to addition
to the resin.

Cumene Hydroperoxide (CHP)

CHP is used less frequently than MEKP or BPO, but can be helpful in lowering laminate exotherm
temperatures, such as those seen in thick parts. CHP should be used with HETRON 970/35 vinyl
ester resin. When using CHP with other resins beside HETRON 970/35 resin, care must be taken
to ensure that a thorough cure is obtained, particularly at ambient temperatures. A post cure is
recommended to insure a thorough cure. CHP can also be used with MEKP in ratios such as a
50/50 mixture. Whenever CHP is used as the only initiator (except with HETRON 970/35), it is
recommended that Ashland Technical Service be contacted for specific instructions.

T-butyl Peroxybenzoate
TBPB is a secondary initiator that can be used in addition to MEKP, BPO, or CHP. The
addition of TBPB assists in achieving a higher degree of cure. We recommend TBPB at
0.2%, based on resin. The addition of TBPB to resin will shorten the pot life. Please consult
Ashland Technical Service for more information on TBPB.

PROMOTERS1
In addition to an initiator, at least one promoter is required to make a resin cure at room
temperature. Generally, the promoter is mixed in thoroughly before adding the initiator. The
initiator then reacts with the promoter to cause the resin to gel. Promoter levels can also be
adjusted to shorten or lengthen a gel time as needed.

Cobalt Naphthenate or Octoate2

Cobalt solutions are blue or purple liquids that are used with MEKP and CHP initiator systems. Cobalt naphthenate

When used at temperatures below 70°F (24°C), it is recommended that cobalt be cut in styrene
monomer prior to addition to the resin. Dilution in styrene will prevent small particles of cobalt
from forming and will facilitate uniform mixing. Please note that selected grades of Cobalt
Naphthenate are acceptable according to FDA regulations.

Dimethylaniline (DMA)
Dimethylaniline is a yellow amine liquid with a strong odor. DMA can be used with MEKP, BPO
(ambient cure), and CHP initiator systems. The addition of DMA is not required with MEKP
and CHP systems. However, small amounts of DMA may be used in conjunction with cobalt to
improve Barcol development and/or shorten the cure time at cool temperatures. With ambient
temperature BPO systems, the addition of DMA is required.
5
COMPOSITE POLYMERS
S E C T I O N 2

Diethylaniline (DEA) is another amine that can also be used. DEA is approximately half as
reactive as DMA; therefore, if 0.1% DMA is called for, 0.2% of DEA should be added to achieve
the same reactivity.

Copper Naphthenate
Copper naphthenate is available as a green paste that typically contains 6 - 8% elemental copper. It
is included in a formulation to control the exotherm of blends intended for MEKP catalyzation. If
low hydrogen peroxide containing MEKPs are used, the impact on the peak exotherm is marginal.
However, if standard MEKPs are used, copper naphthenate will lower the exotherm and lengthen
the time from gel to peak, without effecting the gel time. Typical levels of copper recommended for
exotherm control are 0 – 400 ppm. Copper naphthenate should be added to the formulation the
same day the resin is catalyzed. Please review the suggested amounts for Copper Naphthenate in
Appendix A.

INHIBITORS
Inhibitors are used to lengthen the gel time of vinyl ester and polyester resins. Inhibitors are useful
when very long gel times (1-2 hours) are required or when resin is curing quickly due to high tem-
peratures. Some common inhibitors include tertiary butyl catechol (TBC), hydroquinone (HQ),
and toluhydroquinone (THQ).
TBC is typically sold as an 85% solution, but should be further diluted in styrene to a 10%
solution before addition to the resin. HQ and THQ are sold as solids and should be dissolved in
methanol to a 10% solution to be added to the resin. Inhibitors can also be dissolved in propylene
glycol, which greatly reduces the flammability of the solution. It is recommended that inhibitor
solutions be used as soon as possible to insure their full effectiveness.
TBC, HQ, and THQ can be used with MEKP, BPO, and CHP initiator systems. However, care
should be taken not to add too much inhibitor, which could result in permanent undercure, low
Barcol, or reduced corrosion resistance. Recommended inhibitor levels vary from inhibitor
to inhibitor and from resin to resin. A general guide for addition levels is up to 0.30% of a
10% solution. However, Ashland Technical Service should be contacted for instructions on
adding inhibitors to specific resin systems.
Special attention to additives is necessary when fabricating for FDA applications. Title 21
CFR 177.2420 contains a list of FDA approved additives and should be referred to
before adding promoters, inhibitors, initiators or other additives to resins to be used in
FDA applications.
Included in Appendix C and D are lists of suppliers for many of the products described
in this section. These are not the only suppliers of these products. Check with a local
distributor for suppliers in your area.

Safety
Ashland Specialty Chemical does not manufacture cobalt, DMA, DEA, inhibitors or
initiators. Care should be taken to insure that each product is handled safely. The material safety
Dimethylaniline
data sheet and safety instructions on each product should be obtained from the manufacturer
and read and understood before working with the products.

1
WARNING – Promoters should always be mixed thoroughly into the resin before adding the initiator.
If promoters and initiators are mixed directly together, an explosion could result.

2
6% Cobalt octoate can be substituted for 6% cobalt naphthenate to obtain comparable gel times with
HETRON and AROPOL resins.
6
 S E C T I O N 3

Thixotropes, Antimony Oxides and

Other Additives
Thixotropes
Thixotropes, usually fumed silica, are used to thicken resin and reduce drainage, especially on
vertical surfaces. Resins with these additives are generally used in hand lay-up and spray-up
applications. Polyester resins can be purchased with fumed silica already in the resin, or the
customer may add it. Ashland Technical Service should be contacted before adding thixotropes
to vinyl esters or other resins that are to be used in corrosion applications. The use of fumed
silica in hydrofluoric acid, fluoride containing environments, sodium hypochlorite, and sodium
hydroxide environments is not recommended and could result in a decrease in corrosion resistance.
To insure uniform dispersion, fumed silica should be mixed into the resin using a high shear
dissolver or equivalent.

Antimony Oxides
Cured polyester and vinyl ester resins will burn if provided with a sufficient amount of heat and
oxygen. However, certain resins are flame retardant due to the incorporation of halogens in the
backbone of the polymer. This improves the flame-retardant properties of the laminate. With most
flame-retardant resins, adding antimony trioxide or antimony pentoxide can increase the degree of
flame retardancy of the resin. Antimony acts as a synergist and reacts with the halogens to improve
the resin’s flame-retardant properties. The addition of antimony to non-halogenated resins does not
make the resin flame retardant, but instead acts only as filler.
In the U.S. composites industry, the flame and smoke properties of polyester and vinyl ester
resins are most often rated according to the ASTM E-84 tunnel test as performed under strictly
controlled conditions. In this test, industry code officials, fire marshals, and resin suppliers have
categorized red oak as a flame spread of 100 and asbestos cement board a flame spread of zero.

Laminates containing antimony trioxide, antimony pentoxide,

and no antimony oxide.

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COMPOSITE POLYMERS
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A flame spread of less than or equal to 25 is considered a Class I, and less than 75 but greater
than 25 is a Class II. Some resin systems can obtain a Class I flame spread without the addition of
antimony; others require the addition of 3-5% antimony trioxide or pentoxide to achieve a Class I
rating. Laminates made from HETRON® 197 require 3-5% antimony trioxide or pentoxide to
achieve a Class II rating. Flame spread values of specific resins with and without antimony are listed
in Table 1 or in the specific data sheet of the resin in question.
The use of some grades of antimony pentoxide have been shown to increase the gel time of flame-
retardant vinyl ester resins over time. Because of this, when antimony pentoxide is added to the
resin, it should be used within 8 hours to minimize gel drift. Ashland Technical Service should be
contacted for specific recommendations regarding antimony pentoxide. Please note that antimony
trioxide and pentoxide do not lower smoke emissions.

FILLERS
Alumina Trihydrate
Alumina trihydrate is used to improve flame retardancy and reduce smoke emissions of specific
resin systems.
Alumina trihydrate is a fine, white powdered filler which, when added in the proper amount, can
improve flame retardancy of both halogenated and non-halogenated resin systems. When a properly
filled laminate is exposed to fire, the alumina trihydrate decomposes into water vapor and anhydrous
alumina. The water vapor cools the laminate, thus slowing the rate of decomposition or burning.
Alumina trihydrate differs from antimony trioxide in several ways. As mentioned earlier, antimony
trioxide is effective only with halogenated resin systems and is used in small percentages. Alumina
trihydrate can be effective with both halogenated and non-halogenated resin systems, but much
higher filler loadings are required to achieve the desired flame retardance. Consequently, alumina
trihydrate can not be used directly in place of antimony trioxide. The addition of high levels of
alumina trihydrate can produce a higher viscosity system and reduce the physical properties of the
laminate. It can also reduce smoke emissions, especially in non-halogenated systems.
The addition of alumina trihydrate to the corrosion barrier can result in a significant reduction in
corrosion resistance. Before using alumina trihydrate in corrosion applications, contact Ashland
Technical Service for specific recommendations.

Other Fillers
Calcium carbonate and kaolin clays may also be used as fillers or extenders for polyester and vinyl
ester resins. These materials increase the stiffness of the FRP while reducing the overall cost of the
part. These fillers are not, however, recommended in applications requiring corrosion resistance.
Contact HETRON Technical Service for specific recommendations.

Intumescent Coatings
Intumescent coatings are also used to improve flame retardancy and reduce smoke emissions of
specific resin systems.

Ultraviolet Stabilizers
FRP structures that are placed outdoors may experience surface chalking and/or discoloration.
This chalking and/or discoloration is a surface phenomenon only and should not be detrimental
to properly fabricated equipment. Polyester resins are inherently more ultraviolet (UV) stable than
vinyl ester resins, and the addition of UV stabilizers to the outermost resin layer may reduce UV
degradation. The recommended level of UV stabilizers for use with polyester and vinyl ester resins
is 0.25-0.5%. For halogenated resin systems, the recommended level of UV stabilizer is 0.5%.

8
 S E C T I O N 3

Another option for decreasing UV degradation is HETROLAC® 105 protective lacquer.

HETROLAC 105 is a very low viscosity lacquer containing UV absorber. HETROLAC 105
lacquer improves weather resistance of new FRP. For more information on HETROLAC 105
lacquer, consult the technical data sheet or contact Ashland Technical Service.

Air Release Agents

Air release agents can be added to the resin (0.05-0.5%) to decrease foaming. Excessive levels of
air release agents can cause a laminate to be cloudy, therefore recommended levels should not be
exceeded. Contact Ashland Technical Service for additional information.

Wax Topcoats
Some resins are subject to surface inhibition when cured in the presence of air. Air inhibition affects
the cure and corrosion resistance of the outermost resin layer, which results in an acetone-sensitive,
potentially tacky surface. A wax-containing topcoat approximately 2.0-3.5 mil (51-89 µm) thick
applied to the outermost resin surface can help prevent air inhibition. As the resin cures, the wax
migrates to the surface of the laminate, hardens and prevents air from reaching the laminate. In
conditions under hot sunlight, the wax topcoat may be ineffective. A resin/wax solution should
never be applied between laminate layers, as this could result in poor secondary bonding and
premature failure.
The wax/styrene solution is made by dissolving 20 g of a fully refined paraffin wax (melting point =
130-140°F (54-60°C)) in 180 g of warm styrene (110°F (43°C)). The solution is then added at the
rate of 2% to the resin and mixed thoroughly. The resin solution should then be promoted and
catalyzed as normal. Predissolved wax solutions are also available from FRP distributors.

Abrasion Resistant Additives

An abrasion resistant corrosion liner is necessary when operating conditions involve slurries or other
applications with abrasive particles that can abrade the corrosion liner. When used correctly, silicon
carbide and aluminum oxide have been effective in reducing liner deterioration caused by abrasion.
A mixture of resin and silicon carbide or aluminum oxide should be made and catalyzed based on
resin weight.
The use of carbon veil in place of “C”-glass veil or synthetic veil has also been shown to improve
abrasion resistance. Ashland Technical Service can be contacted for additional information on
improving abrasion resistance.
Included in Appendix C and D are lists of suppliers for many of the additives described in this
section. These are not the only suppliers of these products. Check with a local distributor for
suppliers in your area.

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COMPOSITE POLYMERS
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Reinforcements
Standard Reinforcement Sequence for Corrosion Resistant Equipment
Laminate sequence for standard corrosion resistant equipment is based on the ASTM C581/582
Standard Practice for Determining Chemical Resistance of Thermosetting Resins used in Glass
Fiber Reinforced Structures Intended for Liquid Service. This sequence is illustrated in Figure 2.

Figure 2 Laminate
Figure Corrosion
2. Laminate CorrosionBarrier and
Barrier and Structural
Structural Layer Layer
alternating layers of
primary chopped mat and woven optional
corrosion roving to achieve veil
barrier desired thickness layer

typical
chemical resin/wax
environment topcoat

surfacing veil, 0.010 - 0.020" (0.025 - 0.050mm) thick

chopped strand mat, 0.100 - 0.125" (2.54 - 3.18mm) thick
woven roving

Generally, fabrication begins at the surface that will be exposed to the corrosive environment.
A resin rich layer consisting of 95% resin and 5% reinforcement is applied first. The reinforcement
is in the form of a surfacing veil comprised of C-glass, a synthetic fabric, or carbon fiber. Two plies
of surfacing veil can be used for more severely corrosive environments. The veil is followed by two
or more layers of chopped strand mat, or the equivalent chopped spray. This layer should be at least
100 – 125 mil (2.5 – 3.1 mm) thick and should consist of 20 – 30% glass. Together, the resin, veil,
and chopped glass form the primary corrosion barrier that minimizes penetration of the corrosive
media into the structural portion of the laminate.
The remainder of the laminate, commonly referred to as the structural portion, provides strength
and consists of alternating layers of chopped strand mat and/or chopped strand, and woven roving.
This portion of the laminate should be 40-50% glass. The structural portion of the laminate can
also be filament wound where this layer typically has a minimum of 60% glass. The thickness of
this layer will vary depending on the equipment being fabricated. A final wax topcoat or gelcoat is
then applied to the exterior of the equipment to prevent air inhibition.

10
 S ESCETCI TO I NO N0 4

Types of Reinforcements
The following discussion provides general guidelines for fiberglass selection. However,
the glass manufacturer should be contacted for specific recommendations. Regardless
of glass type, each should be thoroughly evaluated in a test laminate before beginning
actual fabrication. In the test laminate, the glass should wet readily.
There are four basic forms of fiberglass commonly used with HETRON® and AROPOL™
resins. They are as follows:
Surfacing veil
Chopped strand mat
Woven roving
Continuous strand roving
Fiberglass begins as a molten glass and is formed into filaments by pulling it through
bushings. A strand of glass roving is then formed by simultaneously gathering a large
number of filaments together. “C”-glass veil
The surface of the glass is treated with sizings and binders to facilitate further processing,
maintain fiber integrity, and provide compatibility with various resin systems. After this
treatment, the fibers are further processed into the specific glass types that are described
below.

Surfacing Veil
The purpose of surfacing veil, also referred to as surfacing mat or tissue, is to provide
reinforcement for the resin-rich inner liner of a corrosion barrier that prevents cracking
and crazing. A second purpose is to prevent protrusion of the chopped strand mat fibers
to the surface, which could allow wicking of the environment into the laminate to occur.
These are both concerns in aqueous environments.
The primary type of surfacing veil used in corrosion applications is “C”- glass veil.
However, in applications where “C”- glass veil is not suitable, other veil types made from
thermoplastic polyester or carbon fibers may be used.
“C”-glass veil is typically recommended for most corrosion environments. However,
synthetic veil is preferred in some environments, such as those containing fluoride
compounds. Synthetic veil is preferred in other environments, which are noted in the resin NEXUS ® synthetic surfacing veil
selection guide. When using synthetic veil with less flexible resins such as chlorendic
polyesters, a non-apertured synthetic veil type is recommended to minimize stress in the
system. Both non-apertured and apertured synthetic veils can be used with more flexible
resin systems such as vinyl esters.
In severe environments, multiple plies of veil may be recommended, however, caution is
advised. In applications requiring synthetic veil next to the chemical environment, a ply of
“C”-glass veil may be placed behind the synthetic veil to minimize air entrapment and to
assist in making lay-up easier.
Carbon veil is often used in abrasive environments. When used properly, carbon veil has
been shown to provide better abrasion resistance than either “C”-veil or synthetic veil.
Carbon veil is also used to provide a conductive liner for static electricity control. For
applications where conductivity is not desirable, the use of carbon veil should be
reevaluated. Veils made with other types of glasses, such as “A” and “ECR,” are used less
often in the corrosion industry but may be acceptable in certain applications. Thorough
testing should be conducted in the specific environment before using “A” and “ECR” veil.

Carbon veil
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COMPOSITE POLYMERS
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Chopped Strand Mat

Two primary types of chopped strand mat are used in the corrosion industry, “E” and
“ECR” glass. Chopped strand fibers are generally 1/2" – 2" (12.5 – 50mm) long and, after
being chemically treated, are held together by a binder. Together, the glass fiber bundles
form the chopped strand mat. Chopped strand mat is available in a variety of thicknesses:
0.75 oz., 1.5 oz. and 2.0 oz. (225 g/m2, 450 g/m2, 600 g/m2) are used most often in
corrosion applications.

Woven Roving
Woven roving consists of continuous glass fiber rovings that are woven together to form
a heavy mat which is available in a variety of thicknesses and weights. Alternating layers
of woven roving and chopped strand mat are used in the structural portion of hand
lay-up laminates.

Continuous Strand Roving

Chopped strand mat
Most continuous strand roving comes as unwoven strands of glass wound into a
cylindrical package for additional processing. Continuous strand roving is used
in filament winding and pultrusion, or can be chopped into fibers for spray-up
applications to replace chopped strand mat.

Woven roving

Continuous strand roving

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 S E C T I O N 5

Resin Preparation
FDA Compliance
Several HETRON® and AROPOL™ resins comply with FDA regulation Title 21 CFR 177.2420
for repeated use in contact with food, subject to user’s compliance with the prescribed limitations of
that regulation:
HETRON 700, 922, 922L-25 and 942/35 resins
AROPOL 7241T-15, 7334T-15 resins
When fabricating equipment for FDA compliance, contact Ashland Technical Service for addi-
tional resins that meet these requirements.
When fabricating such equipment, there are several steps that should be followed in order to reduce
residual styrene. Prior to exposure, all fabricated equipment should be post-cured at 180°F (82°C)
with dry heat for 4 hours. The surface of the equipment should then be washed with a mild
detergent and water and rinsed thoroughly with water.

Promoter and Initiator Addition

When fabricating with HETRON and AROPOL resins, it is important to promote and catalyze
the resin correctly in order to insure an appropriate working time. Promoter and initiator addition
tables for many HETRON and AROPOL resins are shown in Appendix A. These tables indicate
levels to be added at different temperatures to achieve desired working times. These tables serve
only as guidelines and the values should not be considered specifications. One of the most effective
ways to control the exotherm without effecting the gel time is to add up to 400 ppm of copper
naphthenate to the solution. This should be done as close to the time of catalyzation as possible.
Over time, copper naphthenate and cobalt will react with one another. If a low hydrogen peroxide
initiator is used (BPO, CHP, or any of the “non-foaming” MEKP’s), the gel time will be affected
substantially. HETRON F-Cat epoxy VERs will not foam with standard MEKP’s.

Adjusting Promoter/Initiator Levels for Practical Applications

The levels given in Appendix A represent laboratory conditions and will most often have to be
adjusted to accommodate actual working conditions in a fabricating shop or in the field. Many
things can influence the working time of a resin. High resin and shop temperatures, direct sunlight,
and thick laminates can cause the gel time of a resin to shorten. Low resin and shop temperatures,
heat sinks (metal molds), and fillers can cause the gel time to lengthen.
When the gel time is too short due to working conditions, promoter levels can be adjusted in order
to lengthen the gel time. An inhibitor should be in accordance with those recommended in the
appropriate table.
A summary of some of the most common problems encountered with room temperature cure
systems and suggestions for minimizing these problems is shown in Appendix E. Also, Ashland

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COMPOSITE POLYMERS
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Technical Service can be contacted for assistance in adjusting gel times.

Preparing the Resin

In order to fabricate equipment correctly, the resin must be prepared properly and in a safe manner.
Below are several steps that should be followed when preparing the resin.
1. Estimate the amount of time required for fabrication. Remember to take into account resin
and air temperature: warmer temperature – faster cure; cooler temperature – slower cure. The
viscosity of the resin can also be affected by temperature.
2. If utilizing a neat resin and adding a thixotrope, the thixotrope should be added to the resin
and agitated using a high shear mixer until the desired thixotrope index has been achieved.
High shear agitation generates heat; therefore, this step should be done before adding
any promoters.
3. Using the promoter/initiator addition tables as guidelines, choose the appropriate additive
levels to achieve a suitable working time.
4. Weigh the required amount of resin, cobalt, DMA, and if applicable, inhibitors (predissolved
in styrene or other appropriate solvent) into separate containers. A conversion table is shown
in Appendix F that may be helpful when measuring materials volumetrically.
5. Add the cobalt to the resin and mix thoroughly using an air driven mixer under slow to
moderate agitation. During all mixing, care should be taken to minimize air entrapment
in the resin. Excessive air bubbles in a laminate can cause a reduction of physical and
corrosion properties.
6. Add the DMA or DEA; mix thoroughly.
7. Add any additional liquid materials, such as
inhibitors, and mix thoroughly.
8. Add any pigments or fillers, such as antimony
trioxide, alumina trihydrate, etc., and mix thoroughly.
9. After all ingredients have been added, the
drum should be mixed thoroughly.
10. After mixing in required promoters and fillers,
a sample of resin should be removed and a
gel time test performed. Again, refer to the Applying 6% cobalt naphthenate
designated promoter/initiator table for
recommended initiator level.
11. The gel time can be lengthened by adding an
inhibitor or shortened by adding additional cobalt
or DMA; however, do not exceed the recommended
levels for that resin.
12. Catalyze the resin as needed.
13. If the exotherm of cure is too hot, copper
naphthenate can be added to control this. The gel
time will not be effected if using a standard MEKP.
If more than a combined 400 ppm copper
naphthenate and inhibitor is added to the resin,
a full cure may not be possible. Contact Ashland
Technical Service for further guidelines.
Typical gel timer
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 S E C T I O N 5

Making a Test Laminate

Below is a step-by-step procedure for making a standard test laminate. Materials that will be
needed include release film, a spreading device, a serrated roller, resin, glass surfacing veil, chopped
fiberglass mat, woven roving, and a cleaning solvent. Before beginning the laminating process, the
fiberglass should be cut to the required size and the required amount of resin should be properly
formulated. Do not catalyze the resin until you are ready to begin laminating.

1. The surface should be prepared by

1 2
spreading a release film on the bench top
for protection.
2. At this time, catalyze the amount of
resin to achieve the desired resin-to-glass
ratio. Pour some onto the release film
and spread with the spreading device
(tongue depressor, paint brush, etc.).
When laminating, veil and glass should
be applied to a resin-rich mold surface.
Air bubbles form readily when glass is
applied to a dry surface.

3 3. Carefully position the surfacing veil over 4

the resin and roll with the roller until the
veil is entirely wet out. When rolling out
a laminate, roll firmly, but not too hard,
and roll from the center out to the edges.
This helps “push” the air bubbles out of
the laminate.
4. Apply additional resin and spread with the
spreading device. Make sure that all air
bubbles are removed from the current glass
layer before applying another layer of glass.

5 5. Place one ply of chopped fiberglass 6

mat on the resin and roll with the roller.
If necessary, apply additional resin to
thoroughly wet the mat.
6. Apply a second ply of chopped fiberglass
mat and roll thoroughly. Again, additional
resin can be added if necessary.

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COMPOSITE POLYMERS
S E C T I O N 5

7. When the mat is wet out completely, apply

additional resin, spread with the spreading
devise and apply a layer of woven roving.
Woven roving is more difficult to wet out 7
than veil and mat, therefore, additional resin
and rolling may be required to thoroughly
wet the roving.
8. Repeat steps six and seven as necessary to
make the laminate the required thickness.
9. After all woven roving has been applied,
apply a final layer of resin and chopped
strand mat; roll thoroughly. When rolling is
completed, place the roller in a cleaning
solvent and allow the laminate to cure
thoroughly. When the laminate is thoroughly
cured at room temperature, post cure as
indicated in the following section.

Post Curing the Laminate

After fabricating FRP equipment, it is important to post cure the equipment in order to insure
that optimum cure has been achieved. Figure 3 illustrates how the post cure temperature affects
the ultimate glass transition temperature (Tg) of a resin.
Ideally, a laminate should be post cured for two hours at a temperature above the heat deflection
temperature (HDT) of the resin. The HDT of most HETRON® and AROPOL™ resins is between
200° and 300°F; therefore, a post cure of two hours at 280°F is suitable for most systems.
Laminates made with HETRON 970/35 should be post cured at 300°F for two hours since it
has an HDT of 297°F. Ashland Technical Service can be contacted for additional information on
post curing.

Figure 3. Glass Transition Temperature (Tg) vs. Post Cure Temperature

300

250

200
Tg (oF)

150

100

50

0
0 50 100 150 200 250 300
HETRON 922 Post Cure Temperature (oF)
HETRON 970/35

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 S E C T I O N 6

Fabrication Methods
Fabrication Standards
The fabrication of FRP equipment is governed by various standards that provide guidelines and
requirements for composition, performance, construction, design and testing methods of such
equipment. The American Society of Testing Materials (ASTM), the National Bureau of Standards
(NBS), and the American Society of Mechanical Engineers (ASME) publish numerous standards
for the fabrication of various types of FRP structures. Some common standards are listed below.
1. ASTM C 581 - Standard Test Method for Chemical Resistance of Thermosetting Resins Used
in Glass Fiber Reinforced Structures
2. ASTM C 582 – Standard Specification for Reinforced Plastic Laminates for Self-Supporting
Structures for Use in a Chemical Environment.
3. ASTM D 2105 – Standard Test Method for Longitudinal Tensile Properties of Reinforced
Thermosetting Plastic Pipe and Tube.
4. ASTM D 2143 – Standard Test Method for Cyclic Pressure Strength of Reinforced
Thermosetting Plastic Pipe
5. ASTM D 2310 – Standard Classification for Machine-Made Reinforced Thermosetting
Resin Pipe
6. ASTM D 2517 – Standard Specification for Reinforced Epoxy Resin Gas Pressure Pipe
and Fittings
7. ASTM D 2562 – Standard Practice for Classifying Visual Defects in Parts Molded from
Reinforced Thermosetting Plastics.
8. ASTM D 2563 – Standard Practice for Classifying Visual Defects in Glass-Reinforced
Plastic Laminate Parts.
9. ASTM D 2924 – Standard Test Method for External Pressure Resistance of Thermosetting
Resin Pipe
10. ASTM D 2925 – Standard Test Method for Beam Deflection of Reinforced Thermosetting
Plastic Pipe Under Full Bore Flow
11. ASTM D 2992 – Standard Method for Obtaining Hydrostatic Design Basis for Reinforced
Thermosetting Resin Pipe and Fittings
12. ASTM D 2996 – Standard Specification for Filament-Wound Reinforced Thermosetting
Resin Pipe
13. ASTM D 2997 – Standard Specification for Centrifugally Cast Reinforced Thermosetting
Resin Pipe
14. ASTM D 3262 – Standard Specification for Reinforced Plastic Mortar Sewer Pipe
15. ASTM D 3299 – Standard Specification for Filament Wound Glass-Fiber Reinforced
Thermoset Resin Chemical Resistant Tanks
16. ASTM D 3647 – Standard Practice for Classifying Reinforced Plastic Pultruded Shapes
According to Composition
17. ASTM D 3917 – Standard Specification for Dimensional Tolerance of Thermosetting Glass
Reinforced Plastic Pultruded Shapes

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COMPOSITE POLYMERS
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18. ASTM D 3918 – Standard Definitions Terms Relating to Reinforced Pultruded Products
19. ASTM D 3982 – Standard Specification for Custom Contact-Pressure-Molded Glass-Fiber
Reinforced Thermosetting Resin Hoods
20. ASTM D 4021 – Standard Specification for Glass Fiber-Reinforced Polyester Underground
Petroleum Storage Tanks
21. ASTM D 4350 – Standard Test Method for Corrosivity Index of Plastics and Fillers
22. ASTM D 4385 – Standard Practice for Classifying Visual Defects in Thermosetting
Reinforced Plastic Pultruded Products
23. ASTM D 5364 – Standard Guide for Design, Fabrication, and Erection of Fiberglass
Reinforced Plastic Chimney Liners with Coal-Fired Units
24. NBS PS 15-69 – Voluntary Product Standard for Custom Contact-Molded Reinforced-
Polyester Chemical-Resistant Process Equipment (out of print)
25. ASME/ANSI RTP-1 – An American National Standard for Reinforced Thermoset Plastic
Corrosion Resistant Equipment
Standards are also used for classifying smoke and flame retardant properties of FRP equipment.
The most frequently referred to fire standards are listed below.
1. ASTM D 635 – Standard Test Method for Rate of Burning and/or Extent and Time of
Burning of Self Supporting Plastics in a Horizontal Position
2. ASTM D 2863 – Standard Test Method for Measuring the Minimum Oxygen
Concentration to Support Candle-Like Combustion of Plastic (Oxygen Index)
3. ASTM E 84 – Standard Test Method for Surfacing Burning Characteristics of Building
Materials
4. ASTM E 162 – Standard Test Method for Surface Flammability of Materials Using a Radiant
Heat Energy Source
5. ASTM E 662 – Standard Test Method for Specific Optical Density of Smoke Generated by
Solid Materials
6. ASTM E 906 – Standard Test Method for Heat and Visible Smoke Release Rates for
Materials and Products
7. UL 94 – Standard for Tests for Flammability of Plastic Materials for Parts in Devices and
Appliances

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 S E C T I O N 6

FABRICATION PROCESSES
Hand Lay-Up
Hand Lay-Up
The hand lay-up process requires little capital investment and is the oldest,
simplest, and most labor intensive fabrication method. Hand lay-up is well
suited for low volume production of equipment and can be used for both the
corrosion barrier and the structural portion. Resin
Reinforcement
This process uses a room temperature cure system where catalyzed resin is
applied to the surface of a mold, then fiberglass, usually veil, chopped mat or Laminate
roving, is placed on top of the resin. The fiberglass is then saturated with the
resin by rolling the surface with a roller. This rolling action also assists in
removing air bubbles that can detrimentally affect laminate performance.
Following rolling, more resin and fiberglass are applied to build up the
corrosion barrier and the structural portion of the laminate. Each consecutive
layer is applied in the same manner as the first.

Spray-Up
Spray-up is a faster process and is less labor intensive than hand lay-up. Several Contact Mold
drawbacks to spray-up include the possibility of more air entrapment, and a
difficulty in controlling variables such as thickness and resin-to-glass ratios.
As with hand lay-up, spray-up can be used for the corrosion barrier and the
structural portion of equipment. The spray-up process is a room temperature
cure process in which continuous strand roving is fed through a chopper gun,
combined with catalyzed resin, and sprayed onto a mold surface. The surface is
then rolled to remove air
Spray Up
bubbles. Additional layers
of resin/glass are applied SPRAY-UP
and rolled to reach the Corrosion Barrier
desired thickness.
A two-pot system can also Chopper/
Spray Gun
be used. In this method,
two containers are used;
one contains resin with
twice the required amount
Chopped
of promoters and no Roving
initiator while the other
Typical spray gun contains resin with twice Laminate
the required amount of
initiator and no promoters. Resin is then drawn from both containers and Resin Catalyst
mixed during the spraying process. Resin used with the two pot system must
be stable when promoted and then catalyzed with high levels of additives. Continuous Strand Roving Mold

Filament Winding
Filament winding is an excellent process for fabricating round equipment, such as tanks, pipes,
ducts, etc. Filament winding is less labor intensive than both hand lay-up and spray-up, and
produces very uniform structures as far as thickness, resin to glass ratio, etc. Filament winding is
recommended only for the structural portion of FRP equipment. The corrosion barrier should be
fabricated using either hand lay-up or spray-up.
Filament winding typically uses a room temperature cure system, but generally with very long gel
times. A resin-rich corrosion barrier is applied to a mandrel and allowed to cure. Continuous strand

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 COMPOSITE POLYMERS
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glass or roving is then pulled through guides, impregnated with resin

and guided onto a rotating mandrel in a helical pattern. This produces
Filament Winding the structural portion of the equipment that is typically 60% glass. The
wind angle formed by this pattern has a direct bearing on the physical
strength of the part. Chopped mat and/or roving may also be applied
to accelerate the build-up of the structural portion.
Laminate
Pultrusion
Mandrel Pultrusion is a continuous process that produces parts with a constant
cross-section, such as I-beams, channels, solid rods, and rails. The
process utilizes glass, resin, filler, peroxides, pigments, and release agent.
The glass reinforcement is fed from spools into a resin bath where the
glass substrate is thoroughly impregnated with the resin mixture.
The wet fibrous material then proceeds through forming guides where
Continuous Strand Roving Resin Applicator excess resin is removed from the glass. If the substrate is thin, it
proceeds to a heated die where the resin mixture gels and cures into its
final shape. A thick substrate proceeds through an R.F. preheating chamber
where the temperature of the resin is brought close to the gelation point of the
system. From here, the material proceeds through a heated metal die where the
resinous mass begins to cure. The glass/resin matrix solidifies into the exact shape of the
cavity of the die being used. Grippers or caterpillar pads then pull the cured material to
a cut off station where it is cut to the desired length. Pultrusion can produce unfilled
parts with glass contents as high as 75% and with very high strengths.

Centrifugal Casting
Centrifugal casting is used in fabricating cylinders with a constant thickness. Molds used
in centrifugal casting are often buffed and polished to a mirror finish. Glass and catalyzed
resin are applied to the inside of a rotating mold. This rotation evenly distributes the glass
and resin against the mold surface.

Resin Transfer Molding

Resin transfer molding (RTM) is a mechanical process using a closed mold system.
Initiator and resin are pumped under pressure from two separate containers into a closed
mold containing glass reinforcement, usually continuous strand mat. The resin is pumped into
Examples of putruded profiles
the mold until excess resin escapes through vent tubes placed at the far end of the flow pattern.
The system is then allowed to cure for a specific period of time, after which the mold is opened
and the part is removed.

Continuous Pultrusion RTM requires low viscosity resin, typically less than 250 cps,
Pulling Device
which can be pumped easily and readily fills the mold and wets
Die the glass. Fillers may also be incorporated into the resin mix for
certain applications. RTM uses either room temperature or elevated
temperature initiator systems. RTM is suitable for medium volume
Finished production and provides a process that is less expensive than
Stock
compression molding and faster than spray-up.
Heat Source
Linings
In some cases, the lining of an FRP structure may be eroded
Continuous Strand Roving, Resin Applicator away, but the structural portion of the equipment may be in acceptable
Mat, or Cloth
condition. In these cases, the existing equipment can be relined to extend its
life span. An FRP lining can also be put in existing steel equipment or applied
over concrete. Whether lining an existing structure or putting in a new lining, the surface must
20
 S E C T I O N 6

be properly prepared in order to insure good bonding between the fiberglass lining and the
existing structure.
The eroded or damaged FRP lining should first be washed to remove large amounts of dirt,
etc., and then ground out back to the structural layer. In lining a steel tank, the surface
should be sandblasted to “white metal.” The blasted metal surface should conform to SSPC-
SP-5 or NACE No.1 white metal blast profiles. In the case of concrete, the portland cement
lattice should be removed to expose stone. Several sanding methods are acceptable; however,
grit blasting and sand blasting are the preferred methods. When lining a concrete structure,
the concrete should be at least 28 days old and completely dry. Sandblasting should be
performed the same as with metal. After blasting, any cracks, pits, etc. should be filled in
with putty, allowed to cure, and then sanded smooth. After all sanding is complete, the
surface should be thoroughly vacuumed to remove all dust and dirt.
The surface of the equipment to be relined should not exceed 100°F (38°C). A uniform
primer coat of resin, 1-3 mil (25-76 µm) thick, is then applied using a paintbrush or other
suitable equipment. The primer coat prevents surface corrosion prior to the application of the
A part made by RTM
laminating resin and also provides a bonding surface for the laminating resin. The primer coat
should be allowed to cure under ambient conditions, 60-100°F (15-38°C) to a tack-free state
before applying the laminating resin. The laminating procedure should follow the primer
application as soon as possible. No condensation should be allowed to form over the primer
coat. If the primer coat is allowed to develop a hard cure, the surface should be lightly sanded
and another primer coat applied prior to applying the laminating resin.

Fabricating Thick Sections

HETRON® epoxy vinyl ester resin systems are designed to work successfully in the fabrication
of thick parts where exotherm temperatures are a concern. When laminating a thick section, first
formulate the promoter package to achieve the desired gel time needed for the application
(see Appendix D for specific formulations). Second, fabricate a test laminate to see if the exotherm
of the resin is going to be too high, resulting in burnt sections of the part. If this is the case,
add copper naphthenate to the formulation up to (but no more than) 400 ppm
(see appendix D for formulation examples and copper naphthenate charge levels).
Resin Transfer Molding
As a result, the resin system will maintain the same gel time characteristics, but the
peak exotherm temperature will be much lower, eliminating the concern for
burning. The resin should be used within a day of charging the copper. Copper
causes the gel characteristics to drift over time.

Finishing Processes
There are a variety of methods available to finish the exterior surface of FRP
equipment. In many cases a topcoat of resin containing a dissolved wax is sprayed,
rolled, or brushed onto the surface of the FRP equipment. This wax forms a film
preventing air inhibition of the resin. Air inhibition can lead to a tacky surface.
However, care must be taken if there is any future laminating to be done, such as
the addition of manways or nozzles because the wax will interfere with secondary
bonding. It must be removed prior to subsequent laminations. This is typically
accomplished by surface grinding.
If the equipment needs to be of a certain color, it may be gel-coated or painted. These coatings
have the added advantages of providing opacity for light-sensitive contents and protection from
the weather for FRP equipment used outdoors.

21
COMPOSITE POLYMERS
S E C T I O N 7

Inspecting a Laminate
FRP composite equipment should be inspected after all fabrication is completed and prior to
putting the equipment into service. If possible, the inspection should be done at the fabricator’s
shop where, if any problems are found, they can easily be repaired. An additional inspection should
be done immediately after installing the equipment to insure that there has been no mechanical
damage as a result of transportation and installation. After installation, periodic inspections should
be performed in order to monitor the integrity of the equipment and determine if and when the
equipment needs to be repaired or replaced.
It is also recommended that the resin type, veil and glass type, method of fabrication, service
conditions and date and place of installation be recorded when the equipment is installed. Keeping
a record of this information is essential when the time comes to repair or reline the equipment.

Visual Inspection
One of the simplest and most effective types of inspection is visual. Many imperfections in a
laminate can be detected by simply holding a light behind the laminate and looking at the
laminate. Air bubbles, laminate uniformity, cracks, and wet out are just a few of the things that
can be detected by looking at a laminate. The table in Appendix G describes some common defects
that can be detected visually, along with steps that can be taken to minimize these defects. For
additional information on inspecting FRP parts and common laminate defects, refer to ASTM C
582 Standard Specification for Contact-Molded Reinforced Thermosetting Plastic (RTP)
Laminates for Corrosion Resistant Equipment or ASTM D 2563 Standard Recommended
Practice for Classifying Visual Defects in Glass-Reinforced Plastic Laminate Parts.
The surface of the laminate should also be carefully examined. A surface that is smooth and
uniform in color is usually an indication of a well-fabricated laminate. There should be no dry
spots or glass fibers protruding from the laminate surface.
Occasionally, a specification will require a section of the structure to be cut out and examined for
liner and structural thickness, voids, interlaminar bonding, and overall uniformity of the laminate.
Areas of high stress can also be detected and usually appear as minute cracks in the cross section.

Barcol Hardness
Barcol hardness values serve as an indication of degree of cure; high values indicating thorough
cure and low values indicating incomplete cure. Barcol values will vary from one resin system to
another and will depend on the type and number of veil layers. Generally, a well fabricated,
well-cured laminate will have a minimum Barcol reading of 30. Please contact Ashland Technical
Service for additional information.
According to ASTM C 581, the recorded Barcol value must be at least 90% of the published
Barcol value for that resin system in order for the equipment to be accepted. Barcol values for
HETRON® and AROPOL™ resins are indicated on the individual product data sheets or can be
obtained from an Ashland Technical Service Representative.
To check Barcol hardness of FRP equipment, refer to ASTM D 2583 Standard Test Method for
Indentation Hardness of Rigid Plastics by Means of a Barcol Impressor.

22
 S E C T I O N 7

Usually high or low Barcol values can be attributed to several factors:

High Barcol Values

1. Laminate surface with high glass content; Barcol tester may be measuring glass.

Low Barcol Values

1. Laminate surface with resin/wax topcoat. Sand off small area of wax coat and measure
Barcol again.
2. Laminate fabricated with synthetic veil.
3. Undercured laminate possibly due to incomplete initiator mixing or incorrect initiator ratios.
4. Testing a curved surface.

Acetone Sensitivity
An acetone sensitivity test can be used in conjunction with the Barcol hardness test to
determine the extent of cure of a laminate. This test consists of rubbing four to five drops of
acetone with a finger on the laminate surface until the acetone evaporates. The laminate surface
should be free of mold release, wax, dust, and dirt. After evaporation, if the surface of the
laminate remains tacky or soft, the laminate is air inhibited and is not thoroughly cured. In
some instances, post curing the FRP part can further cure a laminate and improve Barcol
hardness and acetone sensitivity test results.

Barcol hardness impressor

23
COMPOSITE POLYMERS
S E C T I O N 8

Health, Safety and Regulatory Information

Material Safety Data Sheets
Material safety data sheets (MSDS) are available from Ashland Specialty Chemical on all
HETRON® and AROPOL™ resins. The MSDS contains health and safety information to assist
handlers in developing appropriate product handling procedures to protect employees and
customers. The MSDS should be read and understood by all personnel before handling Ashland
Specialty Chemical products in their facility.
HETRON and AROPOL resins are polymers that are diluted with styrene, or other monomers,
to obtain a workable viscosity. The most common hazardous ingredient in the resins are styrene
or other monomers. The polymer contained in the resin is typically non-hazardous.
Styrene has a pungent odor that is easily detected due to the very low odor detection level of less
than 1 ppm. This is why even thoroughly cured parts may have a residual styrene odor.
Styrene is subject to a number of federal and state regulations that
have the potential to impact facilities using HETRON and AROPOL
resins. Current regulations should be reviewed for each facility before
using HETRON or AROPOL resins.
For the most current and comprehensive information on styrene
health affects, see the following web sites: www. styrene.org or
www.styreneforum.org. Other monomers used in HETRON and
AROPOL resins pose different hazards. As always, consult the product
MSDS for details.

Flammability
HETRON and AROPOL liquid resins are flammable due to the
presence of styrene or other monomers. Liquid resin should be stored
away from heat sources, such as space heaters, open flames, and spark
producing equipment. Smoking in the fabrication area should be
strictly prohibited.
Material safety data sheet Sparks from static electricity can also cause fires. One of the most effective
ways to prevent electrostatic sparking is to properly ground and bond in-plant equipment and
containers. Do not use cutting or welding torches in empty resin drums. They may contain flam-
mable vapors which could ignite.
In the event of a fire involving HETRON or AROPOL resins, the fire should be extinguished
using foam, dry powder, or carbon dioxide.
When HETRON and AROPOL resins burn, toxic gases like carbon monoxide and hydrogen
bromide (brominated resins only) may be given off. For this reason, caution should be used to
avoid inhalation of the fumes. If necessary, a self-contained breathing apparatus should be worn
while extinguishing the fire. Consult the MSDS and your site safety plan for more details.

HEALTH CONCERNS
Skin Contact
Protective gloves and clothing should be worn at all times while handling HETRON and
AROPOL resins. Prolonged or repeated skin contact causes skin irritation and may damage the
skin. If resin comes in contact with skin, it should be washed off immediately with large amounts
of water and soap. If the skin is damaged, seek immediate medical attention. If irritation symptoms
persist, seek medical attention.
24
 S E C T I O N 8

Eye Contact
Eye protection should be worn at all times while handling HETRON® and AROPOL™ resins.
Exposure to liquid or vapor may cause eye irritation. If symptoms such as stinging, tearing, redness,
and swelling develop and persist, seek medical attention.

Inhalation
Inhalation of styrene vapors from HETRON and AROPOL resins should be minimized with
ventilation or other engineering controls. Exposure over the recommended limits may cause
respiratory irritation and central nervous system (CNS) effects. Symptoms of CNS depression
include headaches, nausea, drowsiness, etc. If inhalation symptoms develop, immediately move
the individual away from exposure and into fresh air. Seek immediate medical attention.

Ingestion
Swallowing any amount of HETRON or AROPOL resin may be harmful. Seek medical attention,
Protective clothing
and if possible, do not leave the victim unattended.
such as safety
Chronic Health Effects
In 1987, the International Agency for Research and Cancer (IARC) classified styrene in group 2B
(possibly carcinogenic to humans). This classification was not based on styrene itself, but upon that
of styrene oxide, a metabolite of styrene. The potential for styrene exposure to cause cancer in
glasses, safety
humans has been questioned by many organizations. Current information on this topic is available
on the websites previously mentioned in this section.
shoes and gloves
Resin Spills
Very small resin spills of less than 100 grams can be wiped up with a paper towel or cloth. Spills should be worn
greater than 100 grams and less than 10 gallons should be cleaned up by applying sand or another
appropriate absorbent material on the spilled resin. After the resin is absorbed, the material can be
shoveled into a container and properly disposed. The sticky residue should be removed using hot,
soapy water. Large resin spills greater than 10 gallons should be contained using a dike. The spilled
when handling
resin should be removed using containers and properly disposed.
HETRON and
Storage
Resin in drums should be stored below 80°F (27°C) and away from direct heat sources such as
sunlight and steam pipes. If stored at temperatures above 80°F (27°C), storage life will decrease. AROPOL resins.
Bulk quantities of resin should be stored in stainless steel tanks or tanks lined with epoxy or
phenolic coatings. When storing resins, bubbling dry air or a mix of 5% oxygen and 95% nitrogen
into the bottom of the tank may be desirable to keep inhibitors activated and to maximize shelf life.
Containers should be sealed to prevent moisture pickup and monomer loss.

Disposal
Local, state and federal regulations should be carefully followed when disposing of any hazardous
material. Do not discharge effluent containing this product into lakes, streams, ponds, estuaries,
oceans, or other waters. In some states, completely cured resin parts may be considered
non-hazardous; however, it is recommended that the proper local or state agency be contacted
to confirm the proper method of disposal for cured resin parts. For assistance with your waste
management needs—including disposal, recycling and waste stream reduction, contact Ashland
Distribution, IC&S Environmental Services Group at 1.800.637.7922.

25
COMPOSITE POLYMERS
S E C T I O N 9

Appendix A
Promoter and Initiator Addition Tables

Table 1A – Typical Gel Times for HETRON® 922 Resin with MEKP1
Gel Time Gel Time Gel Time
Temperature 6% Cobalt2
DMA4 Initiator (minutes) (minutes) (minutes)
ºF (ºC) Naphthenate
Delta X-9 DDM-9 HiPoint 90
0.3 0.15 1.25 14.3 21.3 21.9
65 (18) 0.3 0.075 1.25 23.8 30.7 29.4
0.3 0.05 1.25 38.3 39.3 39.4
0.3 0.075 1.25 14.8 17.4 16.8
75 (24) 0.3 0.05 1.25 21.3 23.3 22.5
0.3 0.025 1.25 33.0 34.4 35.7

0.2 0.075 1.25 15.3 17.9 18.3

85 (29) 0.2 0.05 1.25 22.2 23.7 24.2
0.2 0.025 1.25 36.7 37.7 40.8

Table 2A – Typical Gel Times for HETRON 922 Resin with BPO3

Temperature Initiator Gel Time

DMA4
ºF (ºC) (50% BPO Paste) (minutes)

0.70 2.0 17.3

65 (18) 0.50 2.0 23.5
0.30 2.0 37.6
0.50 2.0 15.5
75 (24) 0.30 2.0 25.0
0.15 2.0 49.0

0.30 2.0 17.7

85 (29) 0.20 2.0 24.8
0.10 2.0 36.2
0.30 2.0 17.9

Table 3A – HETRON 922 Resin and Different Levels of Copper at 77ºF

Temperature 6% Cobalt2 Copper Initiator Gel Time Gel to Peak Peak

DMA4
ºF (ºC) Naphthenate (PPM) (Delta X-9) (minutes) (minutes) Exotherm

0.30 0.075 0 1.25 15.6 9.4 322ºF

0.30 0.075 100 1.25 16.0 8.0 284ºF
77 (25)
0.30 0.075 200 1.25 15.8 11.2 248ºF
0.30 0.075 300 1.25 16.6 10.9 228ºF

26
 S E C T I O N 9

Table 4A – Typical Gel Times for HETRON® 942/35 Resin with MEKP1
Gel Time
Gel Time Gel Time Gel Time
Temperature 6% Cobalt2 (minutes)
DMA 4
Initiator (minutes) (minutes) (minutes)
ºF (ºC) Naphthenate HiPoint 90/CHP5
Delta X-9 DDM-9 HiPoint 90
(50/50)
0.35 0.2 1.25 9.3 17.9 18.0 45.6
0.3 0.2 1.25 13.2 21.0 21.5 53.2
65 (18)
0.3 0.1 1.25 19.2 26.3 26.3 61.1
0.3 0.05 1.25 28.1 39.0 39.4 69.7
0.3 0.05 1.25 15.4 17.7 16.4 34.5
75 (24) 0.3 0.02 1.25 28.2 32.1 30.4 69.4
0.2 0.02 1.25 52.4 55.4 55.9 111.6

0.4 0.04 1.25 9.2 11.1 11.0 21.3

0.3 0.03 1.25 18.1 19.6 18.8 40.5
85 (29)
0.2 0.03 1.25 29.1 32.0 29.6 55.5
0.1 0.03 1.25 53.3 58.1 49.5 80.9

Table 5A – Typical Gel Times for HETRON 942/35 Resin with BPO3

Temperature Initiator Gel Time

DMA4
ºF (ºC) (50% BPO Paste) (minutes)

0.50 2.0 16.9

0.40 2.0 19.3
65 (18)
0.30 2.0 23.1
0.20 2.0 35.2
0.40 2.0 11.7
0.30 2.0 15.1
75 (24)
0.20 2.0 21.0
0.10 2.0 44.8
0.30 2.0 11.4
0.20 2.0 18.5
85 (29)
0.10 2.0 41.2
0.05 2.0 176.1

Table 6A – HETRON 942/35 Resin and Different Levels of Copper at 77ºF

Temperature 6% Cobalt2 Copper Initiator Gel Time Gel to Peak Peak

DMA4
ºF (ºC) Naphthenate (PPM) (Delta X-9) (minutes) (minutes) Exotherm

0.30 0.05 0 1.25 13.4 6.3 335ºF

0.30 0.05 100 1.25 11.5 7.1 304ºF
77 (25)
0.30 0.05 200 1.25 12.4 10.0 277ºF
0.30 0.05 300 1.25 11.1 10.3 259ºF

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COMPOSITE POLYMERS
S E C T I O N 9

Table 7A – Typical Gel Times for HETRON® 980/35 Resin with MEKP1
Gel Time Gel Time Gel Time
Temperature 6% Cobalt2
DMA4 Initiator (minutes) (minutes) (minutes)
ºF (ºC) Naphthenate
Delta X-9 DDM-9 HiPoint 90
0.55 0.05 1.25 16.2 18.0 18.0
65 (18) 0.4 0.05 1.25 24.9 27.5 30.6
0.4 0.025 1.25 39.1 40.2 42.0

0.4 0.025 1.25 20.0 20.6 20.5

75 (24) 0.3 0.025 1.25 24.9 26.7 26.4
0.2 0.025 1.25 34.5 35.9 35.4

0.3 0.025 1.25 19.7 20.7 21.4

85 (29) 0.25 0.025 1.25 22.1 23.5 26.5
0.2 0.015 1.25 34.6 35.9 40.5

Table 8A – Typical Gel Times for HETRON 980/35 Resin with BPO3

Temperature Initiator Gel Time

DMA4
ºF (ºC) (50% BPO Paste) (minutes)

0.40 2.0 12.8

65 (18) 0.30 2.0 24.9
0.20 2.0 35.7
0.30 2.0 13.6
75 (24) 0.20 2.0 24.7
0.10 2.0 52.1

0.30 2.0 11.6

85 (29) 0.20 2.0 17.5
0.10 2.0 37.9

Table 9A – HETRON 980/35 Resin and Different Levels of Copper at 77ºF

Temperature 6% Cobalt2 Copper Initiator Gel Time Gel to Peak Peak

DMA4
ºF (ºC) Naphthenate (PPM) (Delta X-9) (minutes) (minutes) Exotherm

0.30 0.02 0 1.25 28.2 14.0 328ºF

0.30 0.02 100 1.25 24.0 13.8 312ºF
77 (25)
0.30 0.02 200 1.25 24.5 16.5 284ºF
0.30 0.02 300 1.25 24.6 22.0 254ºF

Table 10A – Typical Gel Times for HETRON FR 992 Resin with MEKP1
Gel Time Gel Time Gel Time Gel Time
Temperature 6% Cobalt2 (minutes)
DMA4 Initiator (minutes) (minutes) (minutes)
ºF (ºC) Naphthenate HiPoint 90/CHP5
Delta X-9 DDM-9 HiPoint 90
(50/50)
0.2 0.1 1.25 16.2 27.1 26.0 60.8
0.2 0.075 1.25 19.5 30.6 30.9 68.8
65 (18)
0.2 0.05 1.25 26.9 40.0 33.4 76.1
0.15 0.05 1.25 35.7 50.9 47.9 112.4

0.3 0.04 1.25 10.7 12.4 12.7 26.9

0.2 0.04 1.25 16.2 20.5 19.1 39.8
75 (24)
0.15 0.04 1.25 21.6 27.3 25.7 53.5
0.1 0.04 1.25 29.6 37.1 35.8 73.7

0.3 0.05 1.25 7.7 7.9 8.3 18.4

0.2 0.05 1.25 10.7 11.5 12.1 23.7
85 (29)
0.1 0.05 1.25 20.0 25.1 23.5 47.8
0.1 0.05 1.25 29.1 34.6 30.1 62.4

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 S E C T I O N 9

Table 11A – Typical Gel Times for HETRON® FR 992 Resin with BPO3

Temperature Initiator Gel Time

DMA4
ºF (ºC) (50% BPO Paste) (minutes)

0.50 20.6
65 (18) 2.0
0.30 26.0
2.0
0.20 36.2
2.0
0.10 70.1

0.30 2.0 16.3

75 (24) 0.20 2.0 23.6
0.10 2.0 47.7

0.30 2.0 11.3

0.20 2.0 15.9
85 (29)
0.10 2.0 27.3
0.05 2.0 59.4

Table 12A – HETRON FR 992 Resin and Different Levels of Copper at 77ºF

Temperature 6% Cobalt2 Copper Initiator Gel Time Gel to Peak Peak

DMA4
ºF (ºC) Naphthenate (PPM) (Delta X-9) (minutes) (minutes) Exotherm

0.10 0.04 0 1.25 22.6 10.5 341ºF

0.10 0.04 100 1.25 20.2 10.2 317ºF
77 (25)
0.10 0.04 200 1.25 20.2 14.2 310ºF
0.10 0.04 300 1.25 20.6 15.9 288ºF

Table 13A – Typical Gel Times for HETRON FR 998/35 Resin with MEKP1
Gel Time
Gel Time Gel Time Gel Time
Temperature 6% Cobalt2 (minutes)
DMA 4
Initiator (minutes) (minutes) (minutes)
ºF (ºC) Naphthenate HiPoint 90/CHP5
Delta X-9 DDM-9 HiPoint 90
(50/50)
0.25 0.025 1.25 11.6 15.2 14.6 36.7
0.35 0.01 1.25 15.8 16.4 16.1 42.9
65 (18)
0.25 0.01 1.25 24.5 27.3 26.8 66.1
0.35 — 1.25 34.8 36.7 38.3 86.0

0.15 0.05 1.25 6.6 10.1 9.3 21.4

0.3 — 1.25 20.5 21.5 22.4 46.8
75 (24)
0.15 — 1.25 31.4 35.0 35.2 76.1
0.1 — 1.25 51.8 57.6 56.9 115.0

0.3 — 1.25 18.0 18.7 18.7 40.8

85 (29) 0.2 — 1.25 22.0 22.3 23.1 49.2
0.1 — 1.25 37.5 41.3 41.0 84.6

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COMPOSITE POLYMERS
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Table 14A – Typical Gel Times for HETRON® FR 998/35 Resin with BPO3

Temperature Initiator Gel Time

DMA4
ºF (ºC) (50% BPO Paste) (minutes)

0.20 2.0 14.1

0.20 2.0 20.0
65 (18)
0.15 2.0 27.0
0.10 2.0 43.0

0.20 2.0 14.1

0.15 2.0 20.1
75 (24)
0.10 2.0 31.4
0.05 2.0 76.5

0.20 2.0 10.3

0.15 2.0 12.3
85 (29)
0.10 2.0 17.7
0.05 2.0 46.0

Table 15A – HETRON FR 998/35 Resin and Different Levels of Copper at 77ºF

Temperature 6% Cobalt2 Copper Initiator Gel Time Gel to Peak Peak

DMA4
ºF (ºC) Naphthenate (PPM) (Delta X-9) (minutes) (minutes) Exotherm

0.10 — 0 1.25 28.3 13.5 320ºF

0.10 — 100 1.25 31.5 15.2 307ºF
77 (25)
0.10 — 200 1.25 32.8 17.4 286ºF
0.10 — 300 1.25 33.1 21.9 279ºF

Table 16A – Typical Gel Times for HETRON 922L Resin with MEKP1

Temperature Gel Time 6% Cobalt2 Dimethylaniline4 MEKP1

ºF (ºC) (minutes) Naphthenate (phr) (phr)

10 - 20 0.30 0.075 1.25

65 (18) 20 - 30 0.30 0.025 1.25
30 - 40 0.30 0.010 1.25
10 - 20 0.30 0.025 1.25
75 (24) 20 - 30 0.10 — 1.25
30 - 40 0.05 — 1.25

10 - 20 0.30 0.010 1.25

85 (29) 20 - 30 0.05 — 1.25
30 - 40 0.025 — 1.25

Table 17A – Typical Gel Times for HETRON 922L Resin with BPO3

Temperature Gel Time Dimenthylaniline4 BPO3

ºF (ºC) (minutes) (phr) (phr)

10 - 15 0.25 2.00
75 (24) 20 - 25 0.15 2.00
30 - 35 0.10 2.00

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 S E C T I O N 9

Table 18A – Typical Gel Times for HETRON® 992L-25 Resin with MEKP1

Temperature Gel Time MEKP1

ºF (ºC) (minutes) (phr)

40 - 50 1.50
65 (18) 50 - 60 1.25
65 - 75 1.00

15 - 25 1.50
75 (24)
25 - 35 1.00

10 - 20 1.50
85 (29)
20 - 30 1.00

Table 19A – Typical Gel Times for HETRON 970/35 Resin with CHP5 and TBC-856
6% Cobalt2
Temperature Gel Time Dimethylaniline4 TBC-856 CHP5
Naphthenate
ºF (ºC) (minutes) (phr) (phr) (phr)
(phr)
10 - 20 0.50 0.40 — 2.50
65 (18) 20 - 30 0.40 0.10 — 2.00
30 - 40 0.20 0.05 — 1.50
10 - 20 0.20 0.15 — 1.50
75 (24) 20 - 30 0.10 0.05 — 1.00
30 - 40 0.10 0.05 0.02 1.00
10 - 20 0.15 0.05 — 1.50
85 (29) 20 - 30 0.10 0.025 0.02 1.00
30 - 40 0.10 0.02 0.03 1.00

Table 20A – Typical Gel Times for HETRON 970/35 Resin with BPO3

Temperature Gel Time Dimethylaniline4 BPO3

ºF (ºC) (minutes) (phr) (phr)

10 - 20 0.20 2.00
65 (18) 20 - 30 0.15 1.75
30 - 40 0.10 1.25
10 - 20 0.15 2.00
75 (24) 20 - 30 0.10 2.00
30 - 40 0.07 2.00

10 - 20 0.10 2.00
85 (29) 20 - 30 0.10 1.25
30 - 40 0.05 2.00

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COMPOSITE POLYMERS
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Table 21A – Typical Gel Times for HETRON® 980 Resin with MEKP1
6% Cobalt2
Temperature Gel Time Dimethylaniline4 MEKP1
Naphthenate
ºF (ºC) (minutes) (phr) (phr)
(phr)
10 - 20 0.30 0.10 1.25
65 (18) 20 - 30 0.30 0.05 1.25
30 - 40 0.20 0.05 1.25
10 - 20 0.30 0.05 1.25
75 (24) 20 - 30 0.20 0.05 1.25
30 - 40 0.20 0.025 1.25
10 - 20 0.20 0.05 1.25
85 (29) 20 - 30 0.30 — 1.25
30 - 40 0.30 — 1.25

Table 22A – Typical Gel Times for HETRON 980 Resin with BPO3 and HQ7 as an Inhibitor

Temperature Gel Time Dimethylaniline4 HQ7 BPO3

ºF (ºC) (minutes) (phr) (phr) (phr)

30 - 40 0.30 — 2.00
40 - 50 0.25 — 2.00
65 (18)
50 - 60 0.20 — 2.00
70 - 80 0.15 — 2.00

15 - 25 0.30 — 2.00
20 - 25 0.25 — 2.00
75 (24)
25 - 35 0.20 — 2.00
35 - 45 0.15 — 2.00

15 - 25 0.25 — 1.50
20 - 25 0.20 — 1.50
85 (29)
25 - 35 0.15 — 1.50
45 - 55 0.10 — 1.50

15 - 25 0.25 — 1.00
25 - 30 0.20 — 1.00
30 - 40 0.15 — 1.00
95 (35)
40 - 50 0.25 0.005 1.00
50 - 60 0.20 0.005 1.00
70 - 80 0.10 0.005 1.00

Table 23A – Typical Gel Times for HETRON FR990 ZX Resin with MEKP1
6% Cobalt2
Temperature Gel Time Dimethylaniline4 MEKP1
Naphthenate
ºF (ºC) (minutes) (phr) (phr)
(phr)

5 - 15 0.30 0.10 1.50

10 - 20 0.20 0.10 1.50
77 (25) 15 - 25 0.30 — 1.50
20 - 30 0.10 0.10 1.50
25 - 35 0.10 — 1.50

32
 S E C T I O N 9

Table 24A – Typical Gel Times for HETRON® 92 Resin with MEKP1
6% Cobalt2
Temperature Gel Time MEKP1
Naphthenate
ºF (ºC) (minutes) (phr)
(phr)

10 - 15 0.50 1.00
15 - 25 0.30 1.00
75 (24)
25 - 35 0.20 0.90
40 - 50 0.10 1.00

10 - 15 0.30 1.00
15 - 20 0.20 0.90
85 (29)
20 - 25 0.10 1.00
25 - 35 0.20 0.50

10 - 15 0.20 0.90
95 (35) 15 - 20 0.10 1.00
20 - 25 0.20 0.70

Table 25A – Typical Gel Times for HETRON 92FR Resin with MEKP1

Temperature Gel Time MEKP1

ºF (ºC) (minutes) (phr)

30 - 35 1.25
65 (18)
35 - 40 1.00

15 - 20 1.50
75 (24)
20 - 25 1.00

5 - 10 1.50
85 (29)
10 - 15 1.00

Table 26A – Typical Gel Times for HETRON 197 and 197-3 Resin with MEKP1
6% Cobalt2
Temperature Gel Time Dimethylaniline4 MEKP1
Naphthenate
ºF (ºC) (minutes) (phr) (phr)
(phr)
3-6 0.70 0.20 1.90
55 (13) 15 - 25 0.70 — 1.50
35 - 45 0.40 — 15.0
3-6 0.60 0.10 1.25
65 (18) 15 - 25 0.60 — 1.25
35 - 45 0.40 — 1.25

10 - 15 0.60 — 1.25
20 - 25 0.40 — 1.25
75 (24)
30 - 40 0.20 — 0.90
55 -65 0.15 — 0.90

10 - 20 0.40 — 1.25
85 (29) 30 - 40 0.20 — 0.90
40 - 50 0.19 — 0.65

10 -15 0.40 — 1.25

95 (35) 15 - 25 0.20 — 0.90
25 - 35 0.20 — 0.65

33
COMPOSITE POLYMERS
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Table 27A – Typical Gel Times for HETRON® 197 and 197-3 Resins with BPO3

Temperature Gel Time Dimethylaniline4 BPO3

ºF (ºC) (minutes) (phr) (phr)

40 - 50 0.25 2.00
65 (18) 50 - 60 0.20 2.00
75 - 85 0.15 2.00

25 -30 0.25 2.00

30 - 35 0.20 2.00
75 (24)
35 - 45 0.15 2.00
50 - 60 0.10 2.00

20 - 25 0.15 1.50
85 (29) 30 - 35 0.10 1.50
70 - 80 0.05 1.50

20 - 25 0.15 1.50
25 - 30 0.15 1.00
95 (35) 30 - 40 0.10 1.00
40 - 50 0.05 1.50
55 - 65 0.05 1.00

Table 28A – Typical Gel Times for HETRON 197P Resin with MEKP1 and HQ7 as an Inhibitor
6% Cobalt2
Temperature Gel Time MEKP1
Naphthenate
ºF (ºC) (minutes) (phr)
(phr)
25 - 35 — 1.50
65 (18) 35 - 40 — 1.25
40 - 50 — 1.00

10 - 15 0.010 1.25
15 - 20 — 1.25
75 (24) 20 - 25 — 1.00
30 - 40 0.006 1.25
45 - 55 0.008 1.25

5 - 10 — 1.50
85 (29)
15 - 20 — 1.00

Table 29A – Typical Gel Times for HETRON 604T20 Resin with MEKP1

Temperature Gel Time MEKP1

ºF (ºC) (minutes) (phr)

25 - 35 1.75
65 (18)
40 - 50 1.25

10 - 20 1.75
75 (24)
25 - 35 1.00

5 - 15 1.75
85 (29)
15 - 25 1.00

34
 S E C T I O N 9

Table 30A – Typical Gel Times for HETRON® 700 Resin with MEKP1
6% Cobalt2
Temperature Gel Time Dimethylaniline4 MEKP1
Naphthenate
ºF (ºC) (minutes) (phr) (phr)
(phr)

30 - 40 0.50 0.10 1.25

65 (18) 40 - 50 0.40 0.10 1.25
60 - 65 0.30 0.10 1.25

20 - 30 0.50 0.10 1.25

30 - 35 0.40 0.10 1.25
75 (24)
40 - 45 0.30 0.10 1.25
50 - 55 0.20 0.10 1.25

15 - 20 0.40 0.10 1.25

20 - 25 0.30 0.10 1.25
85 (29)
25 - 30 0.20 0.10 1.25
45 - 50 0.10 0.10 1.25

15 - 20 0.30 0.10 1.25

25 - 30 0.20 0.10 1.25
95 (35)
35 - 40 0.10 0.10 1.25
45 - 50 0.10 0.10 1.00

Table 31A – Typical Gel Times for HETRON 700 Resin with BPO3
Temperature
Temperature Gel
Gel Time
Time Dimethylaniline4
Dimethylaniline4 BPO
BPO3
3

ºF
ºF (ºC)
(ºC) (minutes)
(minutes) (phr)
(phr) (phr)
(phr)

25
25 -- 35
35 0.50
0.50 2.00
2.00
65
65 (18)
(18) 35
35 -- 45
45 0.40
0.40 2.00
2.00
50
50 -- 60
60 0.30
0.30 2.00
2.00
15
15 -- 20
20 0.60
0.60 2.00
2.00
20
20 -- 30
30 0.50
0.50 2.00
2.00
75
75 (24)
(24) 30
30 -- 40
40 0.40
0.40 2.00
2.00
40
40 -- 50
50 0.30
0.30 2.00
2.00
50
50 -- 60
60 0.20
0.20

25
25 -- 35
35 0.40
0.40 2.00
2.00
35
35 -- 45
45 0.30
0.30 2.00
2.00
85
85 (29)
(29) 50
50 -- 60
60 0.20
0.20 2.00
2.00
65
65 -- 75
75 0.10
0.10 2.00
2.00
15
15 -- 20
20 0.40
0.40 2.00
2.00
20
20 -- 30
30 0.30
0.30 2.00
2.00
95
95 (35)
(35) 35
35 -- 45
45 0.20
0.20 2.00
2.00
60
60 -- 70
70 0.10
0.10 2.00
2.00

35
COMPOSITE POLYMERS
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Table 32A – Typical Gel Times for HETRON® 800 Resin with HETRON 803L-1 Initiator

Temperature Gel Time HETRON 803L-1

ºF (ºC) (minutes) (phr)

15 - 20 5.0
65 (18) 25 - 30 3.0
30 - 35 2.5

10 - 15 4.0
75 (24)
15 - 20 2.5

5 - 10 4.0
85 (29)
10 - 15 2.5

Table 33A – Typical Gel Times for AROPOL™ 7241T-15 Resin with MEKP1

Temperature Gel Time MEKP1

ºF (ºC) (minutes) (phr)

10 - 15 1.90
60 (15) 25 - 30 1.25
50 - 60 0.65
10 - 15 1.90
70 (21) 15 - 20 1.25
45 - 50 0.65

5 - 10 1.90
80 (27) 10 - 15 1.25
20 - 30 0.65

5 - 10 1.25
90 (32)
10 - 15 0.65

Table 34A – Typical Gel Times for AROPOL 7334T-15 Resin with MEKP1

Temperature Gel Time MEKP1

ºF (ºC) (minutes) (phr)

65 (18) 30 - 35 1.25

75 (24) 15 - 20 1.25

85 (29) 10 - 15 1.25

36
 S E C T I O N 9

Table 40D – Typical Gel Times for AROPOL™ 7334T-15 Resin with MEKP1

Temperature Gel Time MEKP1

ºF (ºC) (minutes) (phr)

65 (18) 30 - 35 1.25

75 (24) 15 - 20 1.25

85 (29) 10 - 15 1.25

Copper Conversion Table

55 gallon drum (450 lbs) 5 gallon pail (40 lbs)

ppm
fl. oz./cc’s or grams cc’s or grams

50 0.35 / 10 0.9

100 0.7 / 20 1.8

150 1.0 / 31 2.7

200 1.4 / 41 3.6

250 1.7 / 51 4.5

300 2.1 / 61 5.4

Notes:
1 Methyl Ethyl Ketone Peroxide, 9.0% active oxygen
2 In Europe, 6% cobalt octoate can be substituted for 6% cobalt naphthenate to obtain comparable gel times. If 12% cobalt octoate
is used, half as much 12% cobalt octoate as 6% cobalt naphthenate should be used to obtain comparable gel times.
3 Benzyl Peroxide Paste, 50% active
4 Dimethylaniline
5 Cumene Hydroperoxide
6 TBC-85 is tertiary butyl catechol, 85% solution
7 Hydroquinone

37
COMPOSITE POLYMERS
S E C T I O N 9

Appendix B
Ashland Specialty Chemical Technical Service Contacts
Country/Region Company/Contact
Address/Phone/Fax

UNITED STATES Ashland Specialty Chemical

HETRON® Technical Service
5200 Blazer Pkwy
Dublin, Ohio 43017
phone: 800.327.8720
fax: 614.790.6157
e-mail: hetron@ashland.com

AUSTRALIA Huntsman Chemical Company Australia

Sommerville Road
P.O. Box 62
West Footscray VIC 3012
phone: 61.3.316.3172
fax: 61.3.316.3579

BRAZIL ARA Quimica, S.A.

Alameda Rio Negro, 1084
Salas M3/M5
Barueri, Saõ Paulo
CEP 06454-000, BRAZIL
phone: 55.11.4195.6777
fax: 55.11.4195.1317
e-mail: www.araquimica.com.br

CHINA Ashland Chemical

Holiday Inn Office Building
45 North Zhongshan Road
Room 1205
Nanjing, CHINA 210008
phone: 86.25.331.8982
fax: 86.25.331.8760
e-mail: ashland@public1.ptt.js.cn

EUROPE Ashland Composite Polymers Division

Via delle Groane, 126
20024 Garbagnate (MI) ITALY
phone: 39.02.3978.8446/8447
fax: 39.02.3978.8413

SAUDI ARABIA Saudi Industrial Resins, Ltd.

Manufacturing Facility
P.O. Box 7764
Al Farsi Center, 9th Floor
Jeddah, SAUDI ARABIA 21472
phone: 966.2.651.8920
fax: 966.2.651.7072

SPAIN Ashland Chemical Hispania, S.A.

Manufacturing Facility
Partida Povet 37
APDO Correo 26
12580 Benicarló, SPAIN
phone: 34.964.471.316
fax: 34.964.473.697

38
 S E C T I O N 9

Appendix C
North American Suppliers
Reinforcements
C-Glass Veil Owens Corning 419.248.8000 www.owenscorning.com
NEXUS Veil Precision Fabrics Group Inc. 800.284.8071 www.precisionfabrics.com
Chopped Mat / Woven Roving Vetrotex (CertainTeed) 800.433.0922 www.vetrotexcertainteed.com
Owens Corning 419.248.8000 www.owenscorning.com
PPG Industries, Inc. 412.434.3131 www.ppg.com
Initiators
MEK Peroxide
HIPOINT 90 Witco Corporation 800.494.8737 www.witco.com
LUPERSOL DDM-9 Elf-Atochem North American Inc. 800.558.5575 www.atofina.com
BUTANOX M-50 Akzo Nobel 800.227.7070 www.akzo-nobel.com
NOROX MEKP-9 The Norac Company, Inc. 626.334.2908 www.norac.com
CADOX M-50 Akzo Nobel 800.227.7070 www.akzo-nobel.com
Benzyl Peroxide
LUPERCO ATC paste Elf-Atochem North American Inc. 800.558.5575 www.atofina.com
Cumene Hydroperoxide
Cumene Hydroperoxide Elf-Atochem North American Inc. 800.558.5575 www.atofina.com

Promoters
6% Cobalt/12% Cobalt OMG Americas, Inc. 216.781.0083 www.omgi.com
Dimethyl Aniline/Diethyl Aniline Buffalo Color Corporation 800.631.0171 www.buffalocolor.com

Inhibitors
Tertiary Butyl Catechol (TBC) Union Carbide Chemicals 800.447.4369 www.dow.com
Hydroquinone (HQ) Eastman Chemical Products, Inc. 615.240.4111 www.eastman.com
Toluhydroquinone (THQ) Eastman Chemical Products, Inc. 615.240.4111 www.eastman.com

Antimony Oxides
Antimony Trioxide Hoechst Celanese Corporation 704.554.3148 www.vectran.com
Antimony Pentoxide PQ Corporation 610.651.4200 www.pqcorp.com

Intumescent Coatings
Intumescent Coatings PPG Industries, Inc. 412.434.3131 www.ppg.com

Fumed Silica
CAB-O-SIL TS-720 or M-5 Cabot Corporation 217.253.3370 www.cabot-corp.com
AEROSIL R200 or R202 Degussa Corporation 201.641.6100 www.degussa.com

UV Stabilizers
For Polyester Resins
CYASORB 5411 Cytec Industries 800.486.5525 www.cytec.com
CYASORB UV-9 Cytec Industries 800.486.5525 www.cytec.com
For Vinyl Esters
CYASORB UV-9 Cytec Industries 800.486.5525 www.cytec.com
TINUVIN 328 Ciba Geigy Corporation 800.431.1900 www.ciba.com
UNIVINUL M-40 BASF Corporation 800.669.2273 www.basf.com

Air Release Agents

BYK A515 BYK Chemie 203.265.2086 www.byk.com
SAG 47 OSi Specialties 800.523.5862 www.osispecialties.com

Abrasion-Resistant Additives
Silicon Carbide Exolon – ESK Company 800 962-1100 www.exolon.com
Aluminum Oxide Degussa Corporation 201.641.6100 www.degussa.com

Air Inhibitors /Suppressants

Fully Refined Paraffin Wax H M Royal 800.257.9452 www.hmroyal.com
Fully Refined Paraffin Wax Moore & Munger 800.423.7071 www.mooremunger.com
BYK S750 BYK Chemie 203.265.2086 www.byk.com

Exotherm Suppressant
Copper Naphthenate OMG Americas, Inc. 216.781.0083 www.omgi.com

Wetting Agents
Tween 20 ICI Chemicals 302.887.3000 www.ici.com
BYK R605 BYK Chemie 203.265.2086 www.byk.com

Check out suppliers online for international contacts!

39
COMPOSITE POLYMERS
S E C T I O N 9

Appendix D
Equipment Suppliers
Chopper Guns/RTM Supplies
Magnum Venus Products 800.448.6035 www.venus-gusmer.com
Glas-Craft 317.875.5592 www.glascraft.com
Binks 888.992.4657 www.binks.com

Barcol Hardness Testers

Barber Colman Company 815.637.3222 www.barber-colman.com

Viscometers
Brookfield 800.628.8139 www.brookfieldengineering.com

Gel Timers
Techne 800.225.9243 www.techneusa.com

Portable Heaters
Master Heaters 800.446.1446 www.masterheaters.com
Vogelzang International Corporation www.vogelzang.com

Pumps & Mixers

Magnum Venus Products 800.448.6035 www.venus-gusmer.com

Rollers, Laminating Accessories

Magnum Venus Products 800.448.6035 www.venus-gusmer.com

40
 S E C T I O N 9

Appendix E
Troubleshooting Guide for Curing Resins at Room Temperature
Check Points
Defect
MEKP or CHP BPO
Resin gelling Reduce cobalt, DMA, or initiator levels, but not below those Reduce DMA and/or BPO levels, but not below those
too quickly recommended for that resin system. recommended for that resin system.
Add inhibitor. Add inhibitor.
Check resin, shop and mold temperature; warm temperatures Check resin, shop and mold temperature; warm temperatures
cause resin to gel faster. cause resin to gel faster.

Resin Reduce DMA and/or initiator levels, but not below those Reduce DMA level, but not below that recommended for that
exotherm too recommended for that resin system. resin system.
high during
Lay up fewer plies at one time to reduce amount of heat DMA/BPO is a hot system. Lay-up fewer plies at one time and
curing
generated during exotherm. Allow to exotherm before adding allow to exotherm before adding additional plies.
additional plies.
Use a 50/50 blend of MEKP/CHP.

Resin gelling Increase promoter/initiator levels, not above those Increase promoter/initiator levels, not above those
too slowly or recommended for that resin system. recommended for that resin system.
will not gel
Reduce or eliminate inhibitor. Reduce or eliminate inhibitor.
at all
Check resin, shop and mold temperature; cool temperatures Check resin, shop and mold temperature; cool temperatures
cause resin to gel more slowly. cause resin to gel more slowly.
Check other additives. Antimony trioxides, fillers, and pigments Check other additives. Antimony trioxides, fillers and pigments
may retard gel time. Mix fillers in just before adding initiator. may retard gel time. Mix fillers in just before adding initiator.
Check mixing. Cobalt may be difficult to mix into resin, Check active level of BPO. Some BPO is not 100% active.
especially if resin is cool. Dissolve cobalt in a small amount of Levels may have to be adjusted to find required level of BPO.
styrene before adding to resin.
Insure proper mixing of all additives.
Check fittings on equipment. Bronze, copper and zinc may
inhibit cure.

Resin not Increase promoter/initiator levels, but not above those Increase promoter/initiator levels, but not above those
getting recommended for that resin system. recommended for that resin system.
hard after
Reduce or eliminate inhibitor. Reduce or eliminate inhibitor.
gelation;
spotty cure. If surface is tacky or acetone-sensitive, a wax topcoat may If surface is tacky or acetone-sensitive, a wax topcoat may
be necessary. be necessary.
Insure proper mixing of all additives. Insure proper mixing of all additives.
Check fittings on equipment. Bronze, copper and zinc may inhib-
it cure.

41
COMPOSITE POLYMERS
S E C T I O N 9

Appendix F
Weight to Volume Conversion Tables
Resin Quantity
Additive
Conversion 1 Gallon 5 Gallons 55 Gallons
(phf)
(8.8 lbs, 4 kg) (44 lbs, 20 kg) (450 lbs, 200 kg)

6% Cobalt
Naphthenate1
fl. oz. 0.15 0.7 7.2
0.10
cc 4 21 212
fl. oz. 0.3 1.4 14
0.20
cc 8 41 423
fl. oz. 0.4 2.1 22
0.30
cc 12 62 634
fl. oz. 0.6 2.8 29
0.40
cc 17 83 849
fl. oz. 0.7 3.5 36
0.50
cc 21 104 1.1L

Dimethylaniline

fl. oz. 0.03 0.15 1.5

0.025
cc 0.9 4.5 46
fl. oz. 0.07 0.35 3.6
0.05
cc 2.1 10 106
fl. oz. 0.1 0.5 5.1
0.075
cc 3.0 15 151
fl. oz. 0.15 0.7 7.0
0.10
cc 4.1 21 212

Methyl Ethyl Ketone

Peroxide
fl. oz. 1.2 6.0 61
1.00
cc 36 178 1.8L
fl. oz. 1.5 7.5 77
1.25
cc 44 222 2.3L
fl. oz. 1.8 9.0 92
1.50
cc 53 266 2.7L
fl. oz. 2.1 11 107
1.75
cc 62 311 3.2L
fl. oz. 2.4 13 122
2.00
cc 71 355 3.7L

Benzyl Peroxide
Paste (50% active)
fl. oz. 1.2 5.8 59
1.00
cc 36 164 1.7L
fl. oz. 1.7 8.6 88
1.50
cc 49 245 2.5L
fl. oz. 2.3 11.5 118
2.00
cc 65 327 3.3L
fl. oz. 2.9 14 147
2.50
cc 82 409 4.2L
fl. oz. 3.5 17 176
3.00
cc 98 491 5.0L
1
In Europe, 6% cobalt octoate can be substituted for 6% cobalt naphthenate to obtain comparable gel times. If 12% cobalt octoate
42 is used, half as much 12% cobalt octoate as 6% cobalt naphthenate should be used to obtain comparable gel times.
 S E C T I O N 9

Appendix G
Visual Acceptance Criteria for Cured Laminates

Defect Description Possible Causes Possible Solutions

Air bubbles, Entrapped air in and between Application of too many plies Apply fewer plies at one time and
Voids glass plies of glass at one time roll thoroughly

Inadequate rolling between Reduce mixing speed

applications
Resin viscosity can be reduced
Vigorous mixing causing by adding 3 - 5% styrene
incorporation of air into resin

High viscosity resin used in

combination with thick glass

Blisters Round, elevated areas of varying Too rapid cure with high exotherm Reduce exotherm of resin
sizes on laminate surface, may may cause separation of mat system by laying up fewer plies
occur individually or in a group surfaces at one time

Presence of moisture in glass, Reduce exotherm by lowering

resin, or filler DMA or initiator level

Insure proper storage of resin,

glass, and filler away from
sources of moisture

Crack Cracks running along laminate Overly resin-rich areas Reduce resin content
either on or just below the surface
Cracks may result from dramatic Monitor and minimize
changes in the temperature temperature fluctuations during
conditions of the equipment equipment operation
(thermal shock cracking)

Resin shrinkage during cure

Delamination Separation of glass layers, occurs Inadequate saturation of glass with Insure glass is completely
particularly in areas of high stress; resin saturated with resin and roll thor-
i.e., small-diameter pipe, knuckle oughly
joints, etc. Application of two layers of woven
roving with no chopped mat in Always use alternating layers of
between woven roving and chopped mat

Application of laminate to an FRP Before applying another FRP

surface that has been allowed to layer, lightly sand areas that have
cure several weeks been cured for long periods of
time
Use of rapid cure systems in small
radii areas In tight radii areas, use a low-
exotherm system to reduce resin
shrinkage and stress build-up
43
COMPOSITE POLYMERS
S E C T I O N 9

Defect Description Possible Causes Possible Solutions

Dry Spots Areas where dry glass fibers are Not thoroughly saturating glass Thoroughly saturate glass with
protruding from laminate with resin resin and roll thoroughly

Fish-eye Mass of foreign material on or near Dirty glass Insure fabricating area is clean
the laminate surface; mass is not
blended into surrounding material Contamination of resin with Properly store resin and glass
foreign material to eliminate contamination

Jackstrawing Initially, laminate appears clear, Incompatibility between resin Thoroughly evaluate compatibility
but as curing occurs, white and glass binder; as resin cures, of resin and glass binder before
blemishes appear in the laminate; binder “phases out,” causing beginning fabrication
individual glass fibers become white, cloudy appearance of
prominent and turn white laminate. Typically occurs when Reduce resin exotherm
glass has PVAc binder. Should
not be used in corrosion barrier. Contact Ashland Technical
Service for assistance in selecting
a glass compatible with specific
resins

Pimple Small, raised area on laminate Dripping resin onto a laminate Thoroughly roll out laminate
surface surface that has already begun before resin begins to cure
to cure
Do not continue rolling if resin
Rolling a laminate surface that has is beginning to cure
begun to cure

44
 S E C T I O N 9

Defect Description Possible Causes Possible Solutions

Scorching/Burning Discoloration of laminate as Generation of very high exotherm Reduce DMA and/or initiator
it cures temperatures due to one (or a levels, particularly if working
combination) of the following - temperatures are high

hot working temperatures, Reduce number of plies laid up

high DMA and/or initiator at one time and allow to cure
levels, laying up too many before applying additional layers
plies at one time

Spotty Cure Laminate surface is soft in some Incomplete or inadequate mixing Adjust mixing to achieve a small
areas while cured hard in others of promoters and/or initiator vortex and good movement of
resin surface

Mix thoroughly after addition of

each additive

Dissolve cobalt in small amount

of styrene before adding to resin

Tacky Surface Laminate surface is tacky to the Incomplete cure caused by air Apply a resin/wax topcoat to
touch or fails to pass acetone inhibition tacky surface (see page 12)
sensitivity test (see page 24)
Cobalt level too low Do not use a resin/wax topcoat if
additional bonding is to be done
to the surface

Increase cobalt level

Wrinkle Crease or wrinkle of glass on or Wrinkling of veil (particularly Use 1 oz. (300 g/m2) or 1 1/2 oz.
near the laminate surface synthetic veil) or glass can occur (450 g/m2) mat where wrinkling
when laminating over uneven is a problem
surfaces or when using stiff,
heavy glass in corners Reduce resin viscosity by adding
3 - 5% styrene

45
COMPOSITE POLYMERS

RESPONSIBLE CARE*
Ashland Specialty Chemical has a strong commitment to our customers, our employees, and to
the communities in which we operate and do business. We believe in maintaining our operations in
a totally safe and an environmentally responsible manner. We’ve focused our efforts on conserving
resources and minimizing hazardous materials in both our working environment and at our
customers’. In addition, we also participate in the industry’s Responsible Care* initiative of the
American Chemistry Council.

QUALITY PLUSSM
Batch to batch uniformity of Ashland’s HETRON® and AROPOL™ resin systems not only means
easier molding, but also consistent performance and quality.
Ashland Specialty Chemical adopted a continuous improvement process called Quality Plus in the
early 1980s. Ashland Specialty Chemical became a quality leader in many industries we serve;
continuous improvement has become an important part of every employee’s training and thinking.
Driven from the top down, this process still guides all of our operations and activities, and the way
we do business.
Notice: All precautionary labels and notices should be fully read and understood by all supervisors, personnel and employees before using. For additional safety and health
information, contact Ashland Specialty Chemical. Purchaser has the responsibility for determining any applicability of a compliance with federal, state and local laws and/or
regulations involving use, particularly in making consumer products.

The information contained herein is correct to the best of our knowledge. The recommendations or suggestions contained in this bulletin are made without guarantee or
representation as to results. We suggest that you evaluate these recommendations and suggestions in your own laboratory prior to use. Our responsibility for claims arising
from breach of warranty, negligence, or otherwise, is limited to the purchase price of the material. Freedom to use any patent owned by Ashland or others is not to be
inferred from any statement contained herein.

Environmental Stewardship • Operational Excellence • Innovative Solutions • Global Team

Ashland Tel: 1.614.790.4399 - Technical Service

Composite Polymers Tel: 1.800.327.8720 - Technical Service
5200 Blazer Parkway Tel: 1.800.523.6963 - Customer Service
Dublin, OH 43017 Fax: 1.614.790.6157 - Technical Service
E-Mail: hetron@ashland.com - Technical Service
Ashland is committed to the continuous evolution of
technology and service solutions that promote health, TM
safety and environmental protection around the world. Trademark, Ashland Inc. ® Registered Trademark, Ashland Inc. * Responsible Care and the
SM
Service mark Ashland Inc. In Canada, Ashland Canada, Inc. Responsible Care logo are regis-
© Copyright 2004, Ashland Inc. A Division of Ashland Inc. tered service marks of the
Registered user of Trademark American Chemistry Council, the
Canadian Chemical Producers'
Association and of other entities
in other countries.

Printed in U.S.A Bulletin #2735-1