NFPA 4 s 2 - - A96 ROP

Report of the Committee on (Log #CP1)

482-1 - (Entire Document): Accept
Combustible Metals & Metal Dusts SUBMITTER: Technical Committee on Combustible Metals &
Dusts
I RECOMMENDATION: Completely revise NFPA 482, Standard for
Robert W. Nelson, Chair the Production, Processing, Handling, and Storage of Zirconium, as
Industrial Risk Insurers, CT shown in the draft at the end of this report.
Rep. Industrial Risk Insurers SUBSTANTIATION: This complete revision has incorporated new
material into the document to reflect changes in process technology
in the zirconium industly and to bring the document into conform-
Roy E. Adams, TIMET, NV ance with the NFPA Manual of Style to assist in making the
Rep. Titanium Development Assn. document more usable, adoptable and enforceable.
Tom Christman, Martin- Marietta Energy Systems, TN COMMITTEE ACTION: Accept.
IL Thomas Currin, Salisbury, NG
Ralph W. Hawk, Gyprus Foote Mineral Co., NC
Edward S. Krupiuski, Marsh & McLennan, lnc., AZ
Kevin M. Laporte, Uni-Wash Inc., MI
Jeff D. Martin, Occupational Health Services, TN
John E. McConaghie, Reade Mfg., Co., NJ NFPA 482
Nell T. Morgan, Naval Undersea Warfare Engr Station, WA
David L. Oberholtzer, Valimet, Inc., CA Stafldard for the Production, Processing,
Rep. The Aluminum Assn.
James A. Robertson, Dow Chemical Co., TX Handling, and Storage of Zirconium
Waldemar Seton, SJO Consulting Engr, OR
John Valiulis, Factory Mutual Research Corp., MA 1996 Edition

NOTICE: An asterisk (*) following the number or letter

Alternates
Ron A. Kitsch, Occupational Health Services Inc., TN
(AlL toJ. D. Martin)
Edward D. Leedy, Industrial Risk Insurers, IL
(Alt. to 1L W. Nelson)
W. Anthony Major, Silberline Mfg., Co., Inc., PA
(Alt. to D. L. Oberholtzer)
LarryJ. Moore, Factory Mutual Research, MA
(Alt. toJ. valiulis)
Nonvoting
Albert Muller, Lebanon, NJ
(Member Emeritus)
Staff Liaison: Martha H. Curtis
This list represents the membership at the time the Committee was balloted
on the text of this edition. Since that time, changes in the membership
may have occurred.
Committee Scope: This Committee shall have primary responsibil-
ity for documents o n safeguards against fire and explosion in the
manufacturing, processing, handlin'" g and storage of combustible
metals, powders and dusts.
The Report of the Tecimical Committee on Combustible Metals &
Metal Dusts is presented for adoption.
This Report was prepared by the Technical Committee on
Combustible Metals & Metal Dusts and proposes for adoption a
complete revision to NFPA 482-1987, Standard for the Production,
Processing, Handling, and Storage of Zirconium. NFPA 482-1987 is
published in Volume 7 of the 1995 National Fire Codes and in
separate pamphlet form.
This Report has been submitted to letter ballot of the Technical.
Committee on Combustible Metals & Metal Dusts, which consists of
14 voting members; of whom 13 voted affirmatively and 1 ballot was
not returned (Mr. Valiulis.)
designating a paragraph indicates explanatory material on that
paragraph in Appendix A.
Information on referenced publications can be found in
Chapter 9 and Appendix C.
Chapter 1 General
1-1 Scope.
1-1.1" This standard shall apply to the production, processing,
handling, and storage of zirconium.
1-1.2 This standard shall also apply to finished parts and those
materials, including scrap, that exhibit the burning characteristics of
zirconium.
1-1.3 This standard shall not apply to the transportation of
zirconium in any form on public highways and waterways, or by air
or rail.
1-1.4 This standard shall not apply to those laboratories handling
hazardous chemicals as definedin NFPA 45, Standard on Fire
Protection for Laboratories Using Chemicals.
1,2" Purpose. The purpose of this standard shall be to provide
requirements addressing the fire and explosion hazards of
zirconium and zirconium alloys in all forms and to outline
requirements for fire prevention and protection.
1-3 Equivalency. Nothing in this standard shall be intended to
prevent the use of systems, methods, or devices of equivalent or
superior quality, strength, fire resistance, effectiveness, durability,
and safety over those prescribed by this standard, provided technical
documentation is made available to the authority having jurisdiction
to demonstrate equivalency and the system, method, or device is
approved for the intended purpose.
14 Applicability. The provisions of this document shall be
considered necessary to provide a reasonable level of protection
from loss of life and property from fire and explosion. They reflect
situations and the state-of-the-art prevalent at the time the standard
was issued. Unless otherwise noted, it shall not be intended that the
provisions of this document be applied to facilities, equipment,
structures, or installations that were existing or approvedfor
construction or installation prior to the effective date of the
document, except in those cases where it is determined by the
authority having jurisdiction that the existing situation involves a
distinct hazard to life or adjacent property.
1-5 Def'mitions. For the purpose of this standard, the following
terms shall have the meanings given below.
Approved.* Acceptable to ihe authority having jurisdiction.
Authority HavingJurisdiction.* The organization, office, or
individual responsible for approving equipment, an installation, or a
proc6dure.

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 N F P A 482 - - A96 R O P
Labeled. Equipment or materials to which has been attached a
label, symbol, or other identifying mark of an organization that is
acceptable to the authority having jurisdiction and concerned with
product evaluation that maintains periodic inspection of production
of labeled equipment or materials and by whose labeling the
manufacturer indicates compliance with appropriate standards or
performance in a specified manner.
Listed.* Equipment or materials included in a list published by an
organization acceptable to the authority having jurisdiction and
concerned with product evaluation that maintains periodic
inspection of production of listed equipment or materials and whose
listing states either that the equipment or material meets
appropriate standards or hasbeen tested and found suitable for use
in a specified m a n n e r
Media Collector. Refers to either a bag house or a filter-type
cartridge collector used for collecting dust.
Shall. Indicates a mandatory requirement.
Should. Indicates a recommendation or that which is advised but
not required.
Zirconium. Refers to either pure metal or alloys having the
generally recognized properties of zirconium metal, including the
fire or explosion characteristics of zirconium in its various forms.
Zirconium Chips.* Particles produced from a cutting, machining,
or grinding operation that are not oxidized and that are not diluted
by noncombustible materials.
Zirconium Dust.* Any finely divided zirconium material 420
microns or smaller in diameter (material passing U.S. No. 40
Standard Sieve) that presents a fire or explosion hazard when
dispersed and ignited in air.
Zirconium F'mes. Zirconium particles typically 20 mesh and below
that can be ignited in a static layer.
Zirconium Powder.* See Zirconium Dust and Zirconium Fines.
Zirconium Sponge.* Zirconium metal after it has been won from
the ore but before it is melted.
Zirconium Swarf. Particles produced from a cutting, machining, or
grinding operation that causes partial oxidation of the parent
material or dilution by other inert materials.
Chapter 2 Sponge Production
2-1 Magnesium Operations. All magnesium storage, handling, and
processing operations in zirconium sponge production operations
shall be in accordance with the requirements of NFPA 480, Standard
for the Storage. HandlinD and Processing of Magnesium Solids and
Powders.
2-2 Plant Construction.
2-2.1 Buildings housing reduction furnaces, boring and cru S hing
facilities, and magnesium refining operations shall be constructedof
noncombustible materials. Consideration shall be given to the
provision of deflagration venting in accordance with current
accepted practices.
2-2.2 Building exits shall comply with NFPA 101®, Life Safety Code~.
2-2.3 Floors in reduction, boring, and crushing buildings shall be
made of noncombustible materials, such as concrete, brick, or steel
plate.
2-2.4 Fittings used on compressed air and inert gas line outlets shall
not be interchangeable to prevent potential explosions caused by
inadvertently using compressed air in place of low pressure inert gas.
2-3 Processing Equipment.
2-3.1 Chlorinators and reduction vessels shall be designed to
prevent water from entering the reaction chamber.
2-3.2 Furnaces shall be ~.ept dry and free of iron scale and other
foreign material.
321
2-3.3 Fuel supply lines, to gas-fired furnaces.
. or other gas-fired
equipment shall be installed and mamtmned in accordance with
NFPA 54, National Fuel Gas Code.
2-$.4* Furnaces shall comply with NFPA 86C, Standard for Indust~ial
Furnaces Using a Special ProcessingAtmospherg and NFPA 86D, Standard
for Industrial Furnaces Using Vacuum as an Atmosphere
2-3.5 All electrically operated or controlledprocessing equipment
shall be installed in accordance with NFPA 70, NationalElectrical
Code~.
2-3.6 Back-up methods or systems shall be provided to allow for the
safe and orderly shutdown of critical processes in the case of primary
system failure.
2-4 Storage of Raw Materials.
2-4.1" Chlorine shall be handled and stored in accordance with
accepted industry practice.
2-4.2 Storage and handling of flammable and combustible liquids
shall be in accordance with NFPA 30, Flammable and Combustible
Liquids Cod~
2-4.3* Bulk containers of zirconium tetrachloride (ZrC14) and
silicon tetrachloride (SiCI4) shall be stored in a well-ventilatedplace
located away from areas of acute hazard. Containers shall be plainly
identified and tightly sealed until used.
2-5 Dust Collection.
2-5.1 Dust resulting from the crushing of zirconium sponge shall be
safely managed to minimize the risk of fires and explosions.
2-5.2 Media collectors shall not be used for the collection of
zirconium sponge fines.
2-5.3 Dry collectors shall be emptied before, or when, 80 percent of
the storage capacity is attained. The maximum volume of zirconium
fines collected before emptying shall not exceed 5 gal (19 L).
2-5.4" Dust collectors for Kroll-distilled material shall be located
outside buildings and shall be provided with deflagration vents.
2-5.5* Fans that handle combustible dust and air mixtures shall be
constructed of nonsparking materials and shall be constructed in
accordance with NFPA 91, Standard for Exhaust Systemsfor Air
Conveying of Materials.
2-6" Personnel Safety Precautions. Personnel involved in reduction
furnace tapping, .removal. of molten
. magnesium
. chloride, and
magnesium refimng and castang shall wear tight-fitting, above-the-
ankle shoes, flame-retardant clothing, heat-resistant gloves, and face
shields.
2-7 Sponge Storage.
2-7.1 Zirconium sponge shall be stored in closed metal containers
with a maximum capacity that is capable of being moved by available
equipment.
2-7.2 Zirconium storage areas shall be kept free of combustible
materials, well-ventilated, equipped with required fire protection
equipment, and plainly marked with NO SMOKING signs.
2-7.3 Where drums are used, storage shall be limited to one-drum
tiers per pallet, with no more than four pallet loads high. Stacked
storage shall be done in such a manner so as to ensure stability.
2-7.4 Aisles shall be provided for maneuverability of material-
handling equipment, accessibility, and to facilitate fire-fighting
operations.
Chapter 3* Zirconium Melting
3-1 Explosion Prevention.
5-1.1 The water supply to crucibles shall be continuously monitored
by a system that automatically interrupts power to the furnace upon
a drop in water pressure or flow. In addition, an emergency source
of cooling water shall be provided and shall be actuated
automatically by flow interlock in tile event of interruption of the
primary cooling water.
 N F P A 482 ~
3-1.2 Water-cooled furnaces shall have the crucible a n d its water
jacket located in a protective concrete vault, or o t h e r m e a n s of
isolation shall be provided to protect p e r s o n n e l a n d to minimize
d a m a g e if an explosion occurs.
3-1.3" T h e u p p e r c h a m b e r of the f u r n a c e shall be provided with a
pressure-relieving device, such as a r u p t u r e disc, to aid in safely
relieving pressure if water enters t h e furnace. T h e release pressure
of t h e pressure-relief device shall be a m a x i m u m of 20 psig (138 kPa
gauge).
3-1.4" A clearance shall be m a i n t a i n e d at all times between the
electrode a n d t h e crucible wall to minimize arcing to the crucible
wall.
3-1.5 T h e f u r n a c e shall be e q u i p p e d with a device that continuously
senses pressure within the furnace. T h e device shall automatically
interrupt power to t h e melting h e a t source in t h e event of an
u n e x p e c t e d s u d d e n rise in pressure.
3-1.6 T h e fllrnace shall be e q u i p p e d with:
(a) Water flow, temperature, a n d pressure sensors on all cooling
systems;
(b) Arc voltage a n d m e l t i n g power recorders;
(c) Electrode position indicators;
(d) Furnace pressure sensors a n d recorders; a n d
(e) Set p o i n t alarms on all systems to warn of a b n o r m a l conditions.
3-2* Casting.
3-2.1 T h e water supply to crucibles shall be m o n i t o r e d continuously
by a system that automatically interrupts power to t h e melting heat
source u p o n a drop in water pressure or flow. In addition, an
e m e r g e n c y source of cooling water shall b e p r o v i d e d a n d shall be
actuated automatically by flow interlock in the event of interruption
of the primary cooling water.
3-2.2 Molds for zirconium casting shall be m a d e of material that is
compatible with m o l t e n zirconium. Molds shall be dried t h o r o u g h l y
a n d stored carefully to prevent a c c u m u l a t i o n of moisture in t h e
molds.
3-2.3 Since m o l d breaks are inevitable, t h e casting c h a m b e r shall be
cooled or sufficiently massive to provide a heat sink, or both, to
a c c o m m o d a t e a spill.
3-2.4 Control consoles for water-cooled melting a n d casting
operations shall be located r e m o t e from melting areas a n d outside
of furnace vaults.
3-2.5* Residue from casting furnaces shall be placed in steel boxes
a n d m o v e d outside the building.
Chapter 4* Mill O p e r a t i o n s
4-1FirePrevention.
4-1.1 Flammable or combustible liquids shall be h a n d l e d in
accordance with NFPA 30, Flammable and Combustible Liquids Code.
4-1.2* All electrically-driven e q u i p m e n t used for sawing, cutting, or
g r i n d i n g operations shall be g r o u n d e d in accordance with NFPA 70,
National Electrical Code.
4-1.3 Z i r c o n i u m chips shall be collected in closed-top metal
containers a n d r e m o v e d daily, as a m i n i m u m , to a safe storage or
disposal area.
4-1.4 Forge presses, heavy grinders, a n d o t h e r milling e q u i p m e n t
o p e r a t e d b y hydraulic systems shall use a less h a z a r d o u s h y d r a u l i c oil
widl a flasb p o i n t greater t h a n 200°F (93°C).
4-1.5 N o n f l a m m a b l e coolants shall be used for wet grinding,
cutting, or sawing operations. T h e coolant shall be filtered on a
c o n t i n u o u s basis, a n d the collected solids shall n o t be p e r m i t t e d to
accumulate in quantities greater t b a n 5 gal (19 L) a n d shall be
m o v e d to a safe storage or disposal area.
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A96 R O P
4-1.6 Flammable or combustible liquid coatings applied to
zirconium shall be u s e d in accordance with the r e q u i r e m e n t s of
NFPA 34, Standard for Dipping and Coating Processes Using Flammable or
Combustible Liquids.
4-1.7 Oily crusbed lathe turnings, raw turnings, a n d drips shall be
collected in closed-top metal containers a n d removed daily, as a
m i n i m u m , to a safe storage or disposal area.
4-1.8 Furnaces or o t h e r beating e q u i p m e n t used for heating
zirconium shall be free of iron scale or residue that could react
exothermically widl t h e metal being beated.
Chapter 5 Machining and Fabrication
5-1" Machining Operations.
5-1.1 Cutting tools shall be of proper design a n d shall be kept sharp
for satisfactory work with zirconium.
5-1.2 N o n f l a m m a b l e coolants or lubricants shall be used to
minimize heat g e n e r a t e d by the cutting operation.
5-2 Welding.
5-2.1 All welding of zirconium shall be carried o u t u n d e r a helium
or argon a u n o s p h e r e , or u n d e r vacuum.
5-2.2* Hot work such as electric arc or gas torch welding shall n o t
be permitted in areas where zirconium powder is produced,
handled, packaged, or stored until all exposed chips, dust, fines, or
powder has been r e m o v e d a n d all e q u i p m e n t cleaned thoroughly.
5-3 Zirconium Dust Collection.
5-$.1" Zirconium dust shall be collected by m e a n s of h o o d s or
enclosures at each dust-producing operation. T h e h o o d s or
enclosures shall be c o n n e c t e d to liquid precipitation separators, a n d
tile suction u n i t shall be installed so that the dust is converted to
sludge without contact, in t h e dry state, with any high-speed moving
parts. [See Figures A-5-3.1(a) through (e).]
5-3.2 C o n n e c t i n g ducts or suction tubes between points of
collection a n d separators shall be completely b o n d e d a n d g r o u n d e d .
Ducts a n d tubes shall be as short aspossible, with no unnecessary
bends. Ducts shall be fabricated a n d installed in accordance with
NFPA 91, Standard forExhaust SystemsforAir Conveying of Materials.
5-3.3 Z i r c o n i u m dust-producing e q u i p m e n t shall be c o n n e c t e d to
dust-separating e q u i p m e n t . Multiple pieces of zirconium dust-
p r o d u c i n g e q u i p m e n t shall be permitted to be c o n n e c t e d to a single
zirconium dust-separating unit. An evaluation shall be m a d e to
d e t e r m i n e ff multiple pieces of dust-producing e q u i p m e n t can be
safely served by a single dust-separating unit.
5-3.4* If the zirconium dust-separating unit is to be used for other
materials, it shall be t h o r o u g h l y cleaned of all incompatible
materials prior to a n d after its use.
5-3..5 Thepower. supply to t h e dust-producing e q u i p m e n t shall be
m t e r l o c k e d w l t h t h e airflow from the e x h a u s t blower a n d the liquid-
level controller of the separator so that i m p r o p e r f u n c t i o n i n g of the
d u s t collection system will s h u t down t h e e q u i p m e n t it serves. A
time-delay switch or equivalent device shall be provided on the dust-
p r o d u c i n g e q u i p m e n t to prevent starting of its motor drive until the
separator is in complete operation a n d several air changes have
swept o u t any residual hydrogen.
5-3.6 H o u s e k e e p i n g (Dust).
5-3.6.1 Systematic cleaning of t h e entire building containing dust-
p r o d u c i n g e q u i p m e n t , including roof m e m b e r s , pipes, conduits,
etc., shall be c o n d u c t e d as conditions warrant. Cleaning m e t h o d s
shall be limited to those m e t h o d s that minimize the probability of
fire or explosion, as d e t e r m i n e d by a person knowledgeable in the
properties of zirconium dust.
5-3.6.2 Due to the i n h e r e n t hazards associated with t h e use of fixed
vacuum-cleaning systems for finely divided zirconium dust, special
e n g i n e e r i n g considerations shall be given to the design, installation,
m a i n t e n a n c e , a n d use of such systems.
 NFPA 482 -- A96 ROP
5-3.7 Sludge from dust separators and vacuum-cleaning system
precipitators shall be removed daily, as a minimum, and be kept
thoroughly wet. Covered, vented steel containers shall be used to
transport collected sludge to a safe storage area or for disposal.
Sludge shall be disposer of in accordance with federal, state, and
local regulations.
Chapter 6* Scrap Storage
6-1 Storage.
6-1.1 Open storage of sheet, plate, forgings, or massive pieces of
scrap presents no fire risk andshall be permitted.
6-1.2 Storage of sponge, chips, fines, and dust that are readily
ignitible shall be isolated and segregated from other combustible
materials and zirconium scrap to prevent propagation of a fire.
Chapter 7* Zirconium Powder Production and Use
7-1 Drying and Storage of Zirconium Powder.
7-1.1" Wetted powder shall be dried at a temperature not exceeding
230°F (110°C).
7-1.2" Drying rooms shall be of Type I construction, as defined by
NFPA 220, Stanclardon Types of Building Construction. Theyshall be
segregated as far as possible from other operations. Deflagration
venting for drying rooms shall be considered.
7-1.5 Zirconium powder shall be stored in sealed containers in well-
ventilated areas, and shall be kept segregated from other
combustibles. The containers shall be protected from damage°
7-2 Zirconium Powder Handling.
7-2.1 Special care shall be taken to prevent spills or dispersions that
produce dust clouds.
7-2.2 , Sintering furnaces that handle zirconium parts that are
fabricated from powder shall be installed and operated in
accordance with NFPA 86C, Standard on Industrial Furnaces Using
Special Processing Atnwspheres. Powder or dust shall not be permitted
to accumulate in the furnace or near the heating elements. Furnaces
shall be operated with inert atmospheres of helium, argon, or under
vacuum.
7-2.3 To minimize d~e risk of fire or explosion hazard in the
handling of zirconium powders, the equipment and processes shall
be designed by people knowledgeable in the hazards of zirconium
powders.
7-2.4 Electrical Installmions. All zirconium powder production,
drying, and packing areas shall be evaluated for fire and explosion
hazards associated with the operation, and shall be provided with
approved electrical equipment suitable for the hazardous location.
The electrical equipment shall be installed in accordance with the
requirements of NFPA 70, NationalElectrical Code.
7-3 Personnel Safety Precautions. Personnel handling zirconium
powder shall wear. nonsparking, shoes and noncombustible or flame-
retardant clothing vathout pockets, cuffs, laps, or pleats where
powder can accumulate.
7-4 Housekeeping Practices. Good housekeeping practices shall be
followed so that accumulations of powder do not occur. Special
attention shall be paid to powder accumulations in crevasses and
joints between walls and floors.
Chapter 8 Fire Prevention and Fire Protection
8-1 Fire Prevention. The provisions of Chapter 8 shall apply to all
zirconium production process, handling, and storage operations.
8-1.1 Buildings shall comply with the applicable provisions of NFPA
IOL Life Safe~ Code.
8-1.2 Sponge discharged from dryers shall be collected in containers
that have no larger than a 4000-1b (1814-kg) capacity. The collection
area shall be well-ventilated and free from other combustible
materials.
323
8-1.3* Hot work permits shall be required in designated areas that
contain exposed zirconium fines, dust, or sponge. All hot work areas
that require a permit shall be thoroughly cleaned of zirconium fines,
dust, or sponge before hot work is performed.
8-1.4" All containers used to receive molten metal, molten
magnesium, molten magnesium chloride, or liquid sodium shall be
cleaned and dried thoroughly before use. All pieces of magnesium
metal shall be clean and dry where charged to reduction furnaces.
8-1.5 Good housekeeping practices shall be maintained. Supplies
shall be stored in an orderly manner with properly maintained aisles
to permit regular inspection and segregation of incompatible
materials. Supplies of materials in zirconium processing areas shall
be limited to amounts necessary for normal operation.
8-1.6 Ordinary combustible materials, such as paper, wood, cartons,
and packing material, shall not be stored or permitted to accumulate
in zirconium pllgrocessin areas unless necessary for the process, and
then only in designatedareas.
8-1.7 Periodic cleaning of zirconium dust and fines from buildings
and machinery shall be carried out as frequently as conditions
warrant. Dust and fines shall be removed to a safe storage or
disposal area. Consideration shall be given to the potential ignition
sources associated with the operation of cleaning and processing
equipment during the cleaning operation.
8-1.8 Periodic inspections shall be conducted, as frequently as
conditions warrant, to detect the accumulation of excessive
zirconium dust, chips, or fines on any portions of buildings or
machinery not regularly cleaned in daily operations. Records shall
be kept of these inspections.
8-1.9 Ordinary combustible materials shall not be discarded in
containers used for the collection of dust, swarf, or chips.
8-1.10 Areas handling flammable and combustible liquids shall be in
accordance with the requirements of NFPA 30, Flammable and
Combustible Liquids Coda
8-1.11 Smoking shall be permitted only in designated areas. No
smoking areas shall be posted with NO SMOKING signs.
8-1.12" Boring, crushing, and drying equipment shall be properly
electrically-bonded and grounded to prevent accumulation of static
electricity.
8-1.13 All electrical equipment and wiring in zirconium production,
processing, handling, and storage facilities shall comply with NFPA
70, National Electrical Code.
8-1.14 Where using tools and utensils in areas handling zirconium
powder, consideration shall be given to the risks associated with
generating impact sparks and static electricity.
8-1.1B, Processing equipment used in zirconium operations shall be
properly electrically-bonded and grounded to prevent
accumulations of static electricity.
8-1.16 Where zirconium is collected or stored in containers,
material-handling equipment with sufficient capability to remove any
container from the immediate area in the case of an emergency shall
be readily available.
8-1.17 Areas used for torch-cutting of massive pieces of scrap shall
be kept free of combustible materials.
8-2" General Fire Protection.
8-2.1 A fire protection plan shall be provided for all areas where
zirconium is processed, handled, used, and stored.
8-2.2* Buildings or portions of buildings of noncombustible
construction principally used for zirconium storage or handling shall
not be permitted to be equipped with automatic sprinkler
protection.
Exception: Sprinkler systems installed in accordance with NFPA 13,
Standard for the Installation of Sprinkler Systems, shall be permitted in areas
where combustibles other than zirconium create a more severe hazard than the
zirconium and where acceptable to an authority having jurisdiction who is
knowledgeable of the hazards associated with zirconium.
 NFPA 482 -- A96 ROP
8-2.3* If required by the authority having jurisdiction, automatic
sprinkler protection, installed in accordance with NFPA 13, Standard
for the Installation of Spnnkler Systoms, shall be provided for offices,
repair shops, and warehouses not used for the storage of zirconium
sponge, fines, or chips.
8-2.4* As an alternative, a specially-engineered fire protection
system specifically designed to be compatible with the hazards
present in the zirconium operation area shall be permitted to be
installed in areas where combustible loading is essential to the
process operation.
8-3 Extinguishing Agents and Application Techniques.
8-3.1 Only listed or approved Class D extinguishing agents or those
tested a n d s h o w n to be effective for extinguishing zirconium fires
shall be permitted. A supply of extinguishing agent for manual
application shall be kept within easy reach of personnel while
working with zirconium. The quantity of extinguishing agents shall
be sufficient to contain anticipated fires.
8-3.2 Agents intended for manual application shall be kept in
identified containers. Container lids shall be kept in place to
prevent agent contamination a n d to keep agent moisture free.
Where large quantities of agent are expected to be needed, a clean,
dry shovel shall be providedwith the container. Where small
amounts ,are needed, a h a n d scoop shall be provided with each
container.
8-3.3 Portable or wheeled extinguishers approved for use on
zirconium fires shall be permitted, and shall be distributed in
accordance with NFPA 10, Standard for Portable Fire Extinguishers.
8-3.4 Portable fire extinguislaers shall be provided in accordance
with NFPA 10, Standard for Portable Fire Extinguishers. Water-based or
CO 2 extinguishers shall not be provide d in areas containing
zirconium sponge, fines, or chips.
Exception: CO 2 extinguishers shall be permitted to be present in zirconium
areas for use on electrical fires. These CO 2 extin~'uishers shall be marked
specifically with, "Not for use on zirconium fires.
8-3.5 The following agents shall not be used as extinguishing agents
on a zirconium fire because of adverse reaction:
(a) Water;
(b) Gaseous-based foams;
(c) Halon; and
(d) Carbon dioxide.
8-3.6 An ABC dry chemical a n d a B:C dry chemical extinguisher
shall not be used as a zirconium fire extinguishing agent, but shall
be permitted to be used on other classes of fires in the area where
zirconium is p r e s e n t
8-3.7* Dry sodium chloride, or other dry chemicals or compounds
suitable for extinguishment or containment of zirconium fires, shall
be permitted to be substituted for Class D fire extinguishers. These
alternative agents shall be stored in a m a n n e r that ensures the
agent's effectiveness. Shovels or scoops shall be kept readily
available adjacent to the containers. All extinguishing agent storage
areas shall be clearly identified. -- - -- - h e r designated agent assumes die role o f the authority having
8-3.8 Zirconium fines shall be segregated by storage in
noncombustible drums.
8-3,9* Where a fire occurs in processing equipment, material feed
to the equipment shall be StOlJped. The-equipment shall be kept in
operation, unless continued operation will spread the fire.
Chapter 9 Referenced Publications
9-1 The following documents or portions t h e r e o f are referenced
within dfis standard and shall be considered part o f the
requirements of this document. The edition indicated for each
reference is the current edition as of tile date of the NFPA issuance
of this document.
9-1.1 NFPA Publications. National Fire Protection Association, 1
Batterymarch Park, P.O. Box 9101, Quincy,/VIA 02269-9101.
NFPA 10, Standard for Portable Fire Extinguishers, 1994 edition.
324
NFPA 13, Standard for the Installation of Sprinkler Systems, 1994
edition.
NFPA 30, Flammable and Combustible Liquids Code, 1993 edition.
NFPA 34, Standard for Dipping and Coating Processes Using Flammable
or Combustible Liquid-s, 1995 edition.
NFPA 45, Standard on Fire Protection for Laboratories Using Chemicals,
1991 edition.
NFPA 54, NationalFuel Gas Code~ 1992 edition.
NFPA 70, National Electrical Code, 1996 edition.
NFPA 86C, Standard for lndust~'ial Furnaces Using a Special Processing
Atmosphere, 1995 edition.
NFPA 86D, Standard for Industrial Furnaces Using Vacuum as an
Atmosphere, 1995 edition.
NFPA 91, Standard for Exhaust Systems for Air Conveying of Materials,
1995 edition.
NFPA 101, Life Safety Cod~ 1994 edition.
NFPA 220, Standard on Types of Building Constructior~ 1995 edition.
NFPA 480, Standard for the Storage, Handling, and Processing of
Magnesium Solids and Powders, 1993 edition.
Appendix A ExplanatoryMaterial
. This. Alpp,_endix
. . is not a p art of the requirernents of this NFPA document but
~s tncludea for mformatwnal purposes only.
A-I-I.I See Appendix B for supplementary information on
zirconium.
A-l-2 See Appendix B for supplementary information on zirconium.
A-I-5 Approved. The National Fire Protection Association does not
approve, inspect, or certify any installations, procedures, equipment,
or materials; nor does it approve or evaluate testing laboratories. In
determining the acceptability of installations, procedures,
equipment, or materials, the authority having jurisdiction may base
acceptance on compliance with NFPA or other appropriate
standards. In the absence of such standards, said authority may
require evidence of proper installation, procedure, or use. The
authority having jurisdiction may also refer to the listings or labeling
practices of an organization concerned with product evaluations that
is in a position t o d e t e r m i n e compliance with appropriate standards
for the current production of listed items.
A-l-5 Authority Having Jurisdiction. The phrase "authority having
jurisdiction" is used in NFPA documents in a broad manner, since
JwhUfisdictionsand approval agencies vary, as do their responsibilities.
ere public safety is primary, the authority having jurisdiction may
be a federal, state, local, or other regional d e p a r t m e n t or individual
such as a fire chief; fire marshal; chief of a fire prevention bureau,
labor department, or health department; building official; electrical
inspector; or others having statutory authority. For insurance
purposes, an insurance inspection department, rating bureau, or
other insurance company representative may be the authority having
jurisdiction. In many circumstances, the property owner or his or
jurisdiction; at government installations, the commanding officer or
departmental official may be the authority having jurisdiction.
A-l-5 Listed. The means for identifying listed equipment may vary
for each organization concerned with product e~;altiation, some of
which do n o t recognize equipment as listed unless it is also labeled.
The authority havihgjuris~liction should utilize the system employed
by the listing organization to identify a listed product.
A-l-5 Zirconium Chips. Zirconium chips vary in ease of ignition and
rapidity of burning, d e p e n d i n g on size and geometry. A light fluffy
chip ignites easily~nd burns vigorouslywhile a heavy, compact chip
ignites with difficulty and burng quite slowly.
A-I-5 Zirconium Dust. See NFPA 497B, Recommended Practice for the
Classification of Class 11Hazardous (Classified) Locations for Electrical
Installations in Chemical Process Areas, or NFPA 497M, Manual for
Classification of Gases, Vapors, and Dusts for Electrical Equipment in
Hazardous (Classified) Locations, for information on explosibility
parameters of combustible dusts.
 NFPA 482 -- A96 ROP
A-I-5 Zirconium Powder. See NFPA 497B, Recommended Practicefor
Classification of Class IZ Hazardous (Classified) Locationsfor Electrical
Installations in ChemicalProcessAreas, or NFPA 497M, Manual for
Classification of Gases, Vapors, and Dusts for ElectricalEquipment in
Hazardous (Classified) Locations, for information on explosibility
parameters of combustible dusts.
A-l-5 Zirconium Sponge. Z i r c o n i u m sponge can contain dust a n d
fines that can b e c o m e airborne w h e n the material is handled. If
p r e s e n t in sufficient quantity, t h e d u s t a n d fines can cause increased
fire risk.
A-2-9.1 NFPA 68, Guidefor Venting of Deflagrations, contains
information on the subject of deflagration venting.
A-2-2.3 Floors s h o u l d be slightly crowned or d r a i n e d to prevent
accumulation of water in t h e vicinity of reduction furnaces.
A-2-3.4 For additional information on ovens a n d furnaces, see
NFPA 86, Standard for Ovens and Furnaces.
A-9-4.1 For information on guidelines for h a n d l i n g a n d storing
chlorine, see The Chlo:4neManuaL (See C-1.3.)
A-2-4.3 Z i r c o n i u m tetrachloride in contact with moist air or water
hydrolyzes to f o r m h y d r o g e n daloride gas a n d hydrochloric acid.
Hydrogen chloride is toxic a n d highly irritating to the respiratory
tract. If n o t immediately removed, zirconium tetrachloride in
contact with t h e eyes or skin will result in a double burn, o n e caused
by the acid, the o t h e r caused by the h e a t of reaction. Any skin that is
contacted by zirconium tetrachloride s h o u l d be wiped immediately
a n d t h e n flushed with a large a m o u n t of water. Eyes splashed with
zirconium tetrachloride s h o u l d also be r u s h e d with copious
a m o u n t s of water.
A-2-5.4 A high-efficiency cydone-type collector presents less hazard
t h a n a bag- or media-type collector and, except for extremely fine
powders, usually open,tes with fairly high collection efficiency.
W h e r e cyclones ark used, the e x h a u s t fan discharges to a t m o s p h e r e
away f r o m other opew,~tions. It s h o u l d be recognized that there are
s o m e instances in ~vhich a centrifugal-type collkctor m i g h t be
followed by a fabric or bag- or medla-type collector or By a scrubber-
type collector where particulate emissions are kept at a low level.
T h e hazards of each kollector s h o u l d be recognized a n d protected
against. In each instance, t h e fan is t h e last e l e m e n t downstream in
the system. Because of the extreme hazard involved with a bag- or
media-type collector, consideration s h o u l d be given to a multiple-
series cyclone with a liquid final stage.
Industry experience has clearly d e m o n s t r a t e d that an eventual
explosion can be expected where a bag- or media-type collector is
used to collect zirconium fines. Seldom, if ever, can t h e source of
ignition be positively identified. In those u n u s u a l instances where it
becomes necessary to collect very small fines for a specific
commercial product, it is customary for t h e p r o d u c e r to employ a
bag- or media-type col)ector. Since this presents a strong explosion
potential, the bag- or media-type collector s h o u l d be located a safe
distance from buildings a n d personnel.
If a bag- or media-type collector is used, the shaking system or dust
removal system can be such as to minimize sparking d u e to frictional
contact or impact. P n e u m a t i c or pulse-type shaking is m o r e
desirable because no mechanical moving parts are revolved in the
dusty a t m o s p h e r e . If t h e bags are provided with g r o u n d i n g wires,
they can be positively g r o u n d e d t h r o u g h a low-resistance path to
g r o u n d . W h e r e bags are used, it is customary that the b a g h o u s e be
protected by an alarm that indicates excessive pressure drop across
t h e bags. An excess aiv t e m p e r a t u r e alarm is also frequently used. A
bag- or media-type collector is customarily located a t l e a s t 50 ft (15
m) from any o t h e r building or operation. It is not customary to
permit personnel to be within 50 ft (15 m) of t h e collector d u r i n g
operation or wben shaking bags. Deflagration vents are usually built
into the system, as described in NFPA 68, Guidefor Vev~tingof
Deflagrations. Care is customarily exercised in locating t h e vents
because of the possibility of blast d a m a g e to personne.l or adjacent
structures.
A-2-5.5 Information on spark-resistant fans a n d blowers can be
f o u n d in AMCA Stand;irds H a n d b o o k 99-0410-86, Classificationfor
Spark-Resistant Construction.
A-2-6 Molten m a g n e s i u m a n d molten m a g n e s i u m chloride present
an extremely d a n g e r o u s fire a n d f u m e hazard, in addition to a n
explosion hazard, ff in contact with water or residual moisture.
A-3 Unlike o t h e r metals, which can be melted, cast, or m o l d e d
without u n u s u a l comp]iications, zirconium, because of its strong
affinity for oxygen, hydrogen, mad nitrogen a n d its t e n d e n c y to
b e c o m e c o n t a m i n a t e d is melted in special water or NaK-cooled
325
copper crucibles u n d e r a v a c u u m or with an inert gas blanket of
argon or helium. D u r i n g the early years of t h e zir6onium industry,
melting was d o n e with a n o n c o n s u m a b l e electrode, usually carbon.
T h e c o n s u m a b l e electrode process using direct c u r r e n t electricity
was developed to m e e t q u a l i t / a n d procegs requirements.
D u r i n g the 1950s, several zirconium melting furnace explosions
occurred w h e n water inadvertently e n t e r e d the melting crucibles
d u r i n g t h e melting operation. T h r e e distinct types of explosions
were trident: stea~m kxplosions p r o d u c e d bywAter contacting
molten metal; chemical reaction between the molten metal a n d
water; a n d explosion of free h y d r o g e n g e n e r a t e d by t h e chemical
reaction. Also, if air e n t e r e d the crucibqe at the same time, an air-
hydrogen explosion would s o m e t i m e s occur. All three types of
explosions could occur in the same incident. T h e explosion hazard
is present with any crucible or electrode that is water-cooled.
T h e use of liquid metal NaK (sodium-potassium alloy) as a crucible
coolant has b e e n developed for both laboratory a n d commercial
installations. While the d a n g e r of furnace explosion d u e to leakage
into t h e melt zone is reduced, the h a n d l i n g of NaK has its own
i n h e r e n t hazards. T h e reaction between N a K a n d water is violent.
A-3-1.3 T h e explosion that can occur d u e to the rapid phase
transformation a n d dissociation reaction of water in contact with
m o l t e n material takes place over a time span of aDoroximately 10-5
to 10 -4 seconds. This is faster t h a n a c o n d e n s e d l~)faase detonation.
T h e required pressure-relief device would not be effective in safely
relieving the rapid pressure build-up Caused by t h e rapid phase
transformation. It s h o u l d be n o t e d that the required pressure-
relieving device is i n t e n d e d to safely relieve only m u c h slower
increases in j~ressure, such as m i g h t occur from small incursions of
water onto t h e top of the m o l t e n metal. Following a breech in t h e
v a c u u m system, air will e n t e r t h e f u r n a c e which could create a
secondary explosion d u e to the presence of hydrogen g e n e r a t e d by
the molten metal/water reaction.
A-B-I.4 T h e use of a magnetic field to deflect the electric arc away
f r o m the crucible wall should be considered.
A-3-2 T h e general process for shape casting of zirconium is t h e
"skull-casting" process, where the material to be cast is melted as a
consumable electrode in a tilting crucible. T h e power applied is
normally somewhat h i g h e r t h a n typical for ingot melting in order to
develop, a deep pool of molten, metal. . At t h e appropriate time in the
melting cycle, the electrode Is withdrawn a n d t h e casting poured.
V a c u u m or inert gas is provided to protect the metal from
a t m o s p h e r i c contamination. T h e f u r n a c e crucible is m a d e of
copper a n d has water or NaK cooling. Due to the lfigb power levels
used, seams in the crucible should n o t be e x p o s e d to the electric arc
or the molten metal.
A-3-2.5 Personnel e n t e r i n g furnace shells to c o n d u c t inspections or
repair work should first make certain that any inert gas has been
p u r g e d from t h e shell. See Title 29, Codeof FederalRegulations, Part
1910.146, for Permit Required Confined Spaces. All combustible or
pyrophoric residues s h o u l d be removed or deactivated. These
residues are known to be combustible or pyrophoric mad caution
should be exercised.
A-4 Forging remains the m o s t popular m e t h o d of f o r m i n g
zirconium because it is generally simpler a n d less costly than other
f o r m i n g processes. Gas or electric furnaces with accurate heat
control are used to heat t h e metal into the p r o p e r forging range,
which can vary from 1600°F to 2300°F (871°C to 1260°('). T h e rate
of heat-up a n d final t e m p e r a t u r e often should be controlled
precisely to achieve specific metallurgical a n d physical properties.
Slabs, billets, a n d bar stock are p r o d u c e d by forging.
Large r o u n d s of zirconium are p r o d u c e d by lathe t u r n i n g o r b y
~[rinding forges. A considerable a m o u n t of zirconium strip, coil, mad
staeet, down to foil thickness, is p r o d u c e d from slabs on both
continuous a n d h a n d mills. Wide sheets a n d plates of various
thicknesses are p r o d u c e d on h a n d mills or plate rolling mills.
T e m p e r a t u r e control d u r i n g rolling is important. Shearing a n d
straightening operations are necessary to trim sheet a n d plhte to
size, to straighten or flatten plate, or to straighten forged bar stock
or extrusions. Zirconium vdre is p r o d u c e d f r o m coils of roiled bar
by drawing operations. Fastener stock is p r o d u c e d f r o m coils of
wire. Zirconium tubing is p r o d u c e d by inert gas seam welding of
rolled narrow strip. Heavy wall seamless t u b i n g is p r o d u c e d by
extrusion.
Special types of grinding operations are p e r f o r m e d in mills. Swing
grinders are used to spot grind ingots, slabs, billets, a n d bar stock.
Centerless grinders are used to finish r o u n d bar a n d fastener stock.
 NFPA 482 -- A96 ROP

Strip in coil form is ground continuously mad sheets are individually

ground.
Cold saws mad abrasive cut-off saws are used to cut billet and bar
stock to length. Swarf, or finely divided metal particles, is produced
by all sawing and grinding operations. 1
A-4-1.2 See NFPA 77, Recommended Practice on Static Electrici~ in
operations where static electricity presents a hazard.
A-5-1 Improperlydesigned or dulled tools can produce high
temperatures at the interface, causing ignition at the turnings, if a
sufficient coolant flow is not used. --
A-5-2.2 Cleaning metilodologies should consider d~e hazards of
creating airborne dusts and the dangers associated with the use of
vacuum cleaners.

J Wet collector
E Khau=tet ! S~.-oooningv~t (op~iot~)
Liquid eliminator
plates /
Inlo@clllol*l &i.ld C l i i J l ~ u I %
Ooor Cleanout rJ= _Z_Z
door
el,C~,~tot

i //
51o0¢1 Oo¢~nwarO s i c i l y prates
t o w e r a ColleCtor.
M i k e CJ~-'t IS |hOrt 15
Burring bench
OOU,O4e

Self -oo¢ln,t~g
/,.,.:'F Liquid level
control and
interlock ~ r'l
grilled top
nonsparking material
Clea~!
"\ yen! I K . ,= ., ~ n

--
Ousl pr~,o,tal
el~nl
-',q
elementOUSt
precipitating ~F-',-~'I._. _ _J..,~,'/_..iiquid lev~./~Jl

I
S l u d l l e u t ~ e r llqu,:l
(t,Lb,~OVl~ iriL.l:lUel.lilyl Sludge under" I~ .l I
l
"qu'd ~ IF r 1
I
Figure A-5-3.1 (a) Typical liquid precipitation separator for fixed
dust-producing equipment. Figure A-5-3.1 (b) T yp ical liquid p reel p.itation se p arator for portable
aust-proaucmg equipment.

• I

8°,,...°,no
vent (optional)
I'[':"..- ,-. 7J
Mist eliminator
- - packs

_ _ Mist eliminator
access door
Dust
producing /---- Liquid level control
equipment with interlock

Inspection and
Power to dust F clean out door
producing machine
motor interrupted / - - Water level
by low airflow or low Sludge level
liquid level at the in tank
liquid percipitalor Sump vent
~-- Overflow and drain
piping

Figure A-5-3.1 (c) Typical liquid precipitation separator for fixed dust-producing equipment.

326
 NFPA 482 -- A96 ROP

NOTE: These drawings are schematic and are intended only to

indicate some of the features that are incorporated into the
design o f t separator. The volume of all dust-laden airspace is as
small as possible.

A-5-3.4 For example, iron-oxide dusts are known to be incompatible

with zirconium due to t h e p o t e n t i a l for an exothermic reaction. The
dust-separating unit s h o u l d b e cleaned unless it has been
d e t e r m i n e d that the materials exhibit no incompatibility.
#,-6 Generation of zirconium scrap from the sponge and melting
processes through milling and fabrication is an inherent part of the
zirconium business. Scrap sponge, including some fines, is
generated in the reduction, boring, crushing, leaching, and
blending operations due to contamination and spills. Solid pieces of
scrap zirconium result in the melting process due to air or water
ator contamination or due to malfunctions that cause interrupted melts.
Non sparking _ _ V packs During milling and fabrication, solid pieces of scrap result from
work surface ~ Mist eliminator forging, welding, and fabrication shops. Other scrap includes lathe
turnings and clippings.

Before recycling, lathe turnings and chips are usually crushed,

1/2 in. Expanded [l< <? <"¢"~ < <,~11~ f - Liquidlevel chopped, degreased and compacted with a water-soluble detergent.
metal alum. mesh ~ ! If controlwith Solid scrap is more difficult to handle. A m e t h o d of handling fairly
large chunks of zirconium scrap is to weld them to the sides of
interlock
consumable electrodes prior to melting.

Waler level A more recent development is the nonconsumable electrode

f furnace for melting scrap into ingot form. Equipped with a
continuous feed through a vacuum interlock, these furnaces are
Sludge level capable of handling scrap pieces of baseball size.
in tank
A-7 Not all methods of producing metal powder are applicable to
zirconium. Reduction of zirconium hydride and some forms of
milling are generally used to produce the limited amounts of
powder now required commercially. To reduce oxidation and
possible ignition hazards, milling can be performed underwater or
in an inert atmosphere of helium or argon. Some powders are given
a very light copper coating during the manufacturing process.
A-5-3.1 (d) Typical liquid precipitation separator for portable
dust-producing equipment. Like many other metal powders, zirconium is capable of forming
explosive mixtures in air. The ignition temperatures of dust clouds,
u n d e r laboratory test conditions, range from 626°F to 1094°F (330°C
to 590°C). The minimum explosive concentration is 0.045 oz/ft 3
(0.045 kg/m3). Maximum pressure o r o d u c e d in explosions in a
closed bomb at a concentration of 0.~ oz/ft3 (0.5 kg/m3) ranged
from 46 psi to 81 psi (317 kPa to 558 kPa). The average rate of
pressure rise in these tests ranged from 250 psi/sec to 4300 psi/sec
(1724 kPa/sec to 29,650 kPa/sec); the maximum rate of pressure
rise ranged from 550 psi/sec to 10,000 psi/sec (3792 kPa/sec to over
68,950 kPa/sec). The minimum energy of electrical condenser
discharge sparks required for ignition of a dust cloud was 10
millijoules; for a dust layer, the minimum value was 8 microjoules.
Some samples of zirconium powder were ignited by electric sparks in
pure carbon dioxide, as well as in air. In some cases, zirconium at
elevated temperatures was found to react in nitrogen as well as in
carbon dioxide. Zirconium powder is considered a flarmnable solid.

A-7-1.1 Experience has shown that the tendency for auto-ignition

increases with decreasing particle size of the powder. In particular,
in the range of 40 microns and below, the particles exhibit
pyrophoric tendencies. This tendency is exacerbated in the
presence of moisture.

A-7-1.2 For information on designing deflagration venting, see

NFPA 68, Guide for Venting of Deflagrations.

A-7-2.2 The equipment and processes should be designed with

consideration for the need to minimize the damage to property and
risk to life resulting from fires and explosions involving zirconium
powders. Design considerations should include the use of
deflagration venting, proper dust collection systems, inerting, or a
combination of these. The inert gas used should be d e t e r m i n e d by
test to be appropriate for the zirconium powder being handled.
Zirconium powder can react exothermically in pure carbon dioxide
atmospheres and in pure nitrogen atmospheres.

Tests have shown that the maximum oxygen concentrations

allowed for different inert gases to prevent explosions are:
Argon 4.0 percent oxygen
A-5-3.1 (e) Diagram of five methods of precipitating Helium 5.0 percent oxygen
dust used in precipitators such as those shown in
Figures A-5-3.1(a), (b), (c) and (d).

327
 NFPA 482 -- A96 ROP
This data was obtained from U.S. Bureau of Mines, Report of
Investigations 3722, Inflammability and Explosibility of Metal Powders,
Report of Investigations 4835, Explosive Characteristics of Titanium,
Zirconium, Thorium, Uranium, and Their Hydrides, a n d Report of
Investigations 6516, Explosibility of Metal Powders.
A-8-1.3 For information on cutting a n d welding practices, see NFPA
51 B, Standard for Fire Prevention in Use of Cutting and Welding Processes.
A-8-1.4 Molten m a g n e s i u m a n d m o l t e n m a g n e s i u m chloride p r e s e n t
an extremely d a n g e r o u s fire a n d f u m e hazai-d, in addition to an
explosion hazard, if contacted with water or residual moisture.
A-8-1.12 For information on static electricity, see NFPA 77,
Recommended Practice on Static Electricity.
A-8-1.15 For information on static electricity, see NFPA 77,
Recommended Practice on Static Electricity.
A-8-2 T h e principal intent in fighting zirconium fires is isolation a n d
containment, rather t h a n e x t i n g u i s h m e n L Water a n d o t h e r liquids
have proven ineffective in extinguishing zirconium fires. Streams of
water intensify the fire by f e e d i n g oxygen to it. T h e r e is also the
ossibility of causing a steam or h y d r o g e n explosion, particularly if
rge a m o u n t s of z i r c o n i u m are involved. T h e great affinity of high-
t e m p e r a t u r e zirconium for oxygen will free a considerable a m o u n t
of hydrogen, which can reach explosive concentrations in confined
spaces. E n t r a p m e n t of water u n d e r any b u r n i n g or h o t metal can
result in a steam explosion.
Zirconium fires, being quite u n i q u e in nature, require a
comprehensive fire protection plan where zirconium is processed,
handled, used, or stored. This plan s h o u l d include specific actions
in the event of a zirconium fire a n d s h o u l d be coordinated with t h e
local facility m a n a g e m e n t , r e s p o n d i n g fire fighters, a n d medical
personnel.
This plan s h o u l d pay attention t o the e x t r e m e hazards associated
with zirconium-water reactions that m i g h t occur with sprinkler
water. Specific attention s h o u l d be paid to an evacuation plan for
personnel in the event of any release of water.
Properly trained personnel who work with zirconium know its
hazards. Such personnel will have the greatest chance to extinguish
a zirconium fire in its incipient stage. Training s h o u l d include
sufficient information to d e t e r m i n e if e x t i n g u i s h m e n t can be safely
a n d effectively accomplished.
A-8-2.2 Automatic sprinkler protection should n o t be r e c o m m e n d e d
for b l e n d i n g a n d melting buildings.
A-8-2.3 Water-based extinguishers approved for use on Class A fires
should only be used on fires in ordinary combustibles. Extinguishers
approved for Class B fires are r e c o m m e n d e d for fire in oil, grease,
a n d most flammable liquids. Extinguishers approved for Class C
fires s h o u l d be used for fires in electrical e q u i p m e n t .
A-8-2.4 If dry chemical extinguishing systems are used, see NFPA 17,
Standard for D~y ChemicalExtinguishing Systems.
A-8-3.7 Experience has shown that dry s o d i u m chloride is one of the
most effective chemicals for containing zirconium s p o n g e or fines
fires. Fire-fighting salts s h o u l d be checked periodically to ensure
that they have n o t b e c o m e caked from moisture. A n o t h e r effective
chemical is a nonmetallic flux c o m p o u n d consisting of potassium
chloride, m a g n e s i u m chloride, a n d calcium fluoride. Commercial
dry powder fire extinguishers or agents approved for use on
combustible metals are also effective. Covering the fire completely
reduces t h e accessible oxygen supply, thereby slowing t h e b u r n i n g
rate so that eventual e x t i n g u i s h m e n t is reached.
A-8-3.9 Keeping the e q u i p m e n t in operation until all b u r n i n g
material is r e m o v e d can reduce d a m a g e to the equipment. Small
a m o u n t s of b u r n i n g materials can be h a n d l e d with a shovel to
facilitate removal.
Appendix B Supplementary Information on Zirconium
This Appendix is not a part of the requirements of this NFPA document but
is included for informational purposes only.
B-1 History. Klaproth first reported the discovery of the e l e m e n t
zirconium in 1789, d u r i n g his analysis of t h e precious stone called
jargon. O t h e r chemists c o n f i r m e d his discovery and, in 1797,
Vauquelin reported on s o m e of its properties a n d detailed its
328
preparation. At that time, it was called zirconia. Berzelius first
isolated the i m p u r e metal in 1824, b u t it was not until 1925 that the
ductile metal was p r o d u c e d b y v a n Arkel a n d deBoer, using their hot
wire reduction process.
A commercial scale production process for m a k i n g ductile
zirconium was developed at the U.S. Bureau of Mines Laboratories
where Dr. Wilhelm Kroll served as consultant a n d advisor for the
process that bears his name.
B-2 Properties.
B-2.1" Zirconium is a silvery-gray metal having a close-packed
hexagonal crystal structure at r o o m temperature. At 1584°F
(862°C), the crystal structure c h a n g e s to body-centered cubic. Both
structures are very ductile a n d t h e metal is easily m a c h i n e d , rolled,
a n d e x t r u d e d u s i n g conventional e q u i p m e n t a n d methods.
B-2.2 Some of the chemical a n d physical properties of zirconium
are as follows:
Atomic N u m b e r 40
Atomic W e i g h t 91.22
Atomic Radius 1.60 a n g s t r o m units
Specific Gravity 6.5
Melting Point 3360°F (1850°C)
Boiling Point 6475°F (3580°C)
Electronegativity 1.6
Valence +4*
*in most chemical reactions
B-2.3 Zirconium has a very low capture cross section for thermal
neutrons, 0.18 barns. Its principal alloys have o u t s t a n d i n g resistance
to corrosion in water a n d steam at high temperatures. These
properties make zirconium desirable as a cladding material for fuel
e l e m e n t s in water-cooled nuclear power reactors. However, it
b e c o m e s embrittled a n d loses strength on Ionl~-term exposure to air
at t e m p e r a t u r e s above 1004°F (540°C).
B-3 Combustibility and Explosibillty.
B-3.1 In laboratory tests, a dust cloud of fine particles of zirconium
(average particle diameter of 3.3 microns) ignited spontaneously at
68°F (20°C). Powder having an average particle diameter of 17.9
microns would not ignite u n d e r similar circumstances until heated
to 662°F (350°C). Similar clouds in carbon dioxide h a d to be
heated to 1020°F (650°C) for ignition to occur. In a t m o s p h e r e s of
air a n d helium, at least 5 p e r c e n t oxygen h a d to be present to obtain
spark ignition of zirconium dust clouds.
B-3.2 Layers of zirconium powder on h o t surfaces ignited at 374°F
(109°C) in air; at 1148°F (620°C) in carbon dioxide; a n d at 1454°F
(790°C) in nitrogen.
B-3.3 T h e m i n i m u m explosiv~ concentrat~jon for zirconium dust in
air was fo,p n d to be 0.q4 o z / f t " (40.5 g / r e " ) . At concentrations of
1.0 oz/ft" (1013 g / m ° ) , m a x i m u m explosion pressure was 76 psig to
78 psig (524 kPa to 538 kPa) a n d m a x i m u m rate of pressure ri~e
r a n g e d from 9500 psi/sec to 10,000 p s i / s e c (65,500 k P a / s e c to
68,950 kPa/sec). For f u r t h e r information, see U.S. Bureau of Mines
Reports of Investigations 3722, Inflammability and ExplosibiliO of Metal
Powders, a n d Report of Investigations 4835, Explosive Characteristics of
Titanium, Zirconium, Thorium, Uranium, and Their HydHdes.
B-4 Hazards.
B-4.1 Zirconium a n d its alloys do n o t p r e s e n t serious risk w h e n
h a n d l e d in m o s t forms in which they are ultimatelyused, i.e., tubes,
bars, mad sheets. However, finely divided chips, turnings, or powder
can be easily, sometimes spontaneously, ignited a n d can b u r n very
rapidly. A l t h o u g h other potential hazards exist d u r i n g melting,
those that have resulted in t h e most serious a n d lethal accidents
have been associated with the h a n d l i n g of zirconium powders, finely
divided scrap, a n d so-called black reaction residues. For tl.fis reason,
special precautions m u s t be observed d u r i n g h a n d l i n g or disposal of
ttaese materials.
Several c o m p a n i e s have reported that fires have occurred wlfile
zirconium bars, plates, a n d o t h e r shapes were being chopped. A
n u m b e r of fires have occurred w h e n h o t or b u r n i n g chips fell into
accumulations of moist fines on or u n d e r lathes or milling machines.
The m o s t violent reactions have occurred when b u r n i n g chips fell
into d r u m s or deep containers partially filled with moist turnings or
scrap.
 NFPA 482 1
B-4.2 In the molten state, zirconium either dissolves or is
contaminated by every I~aown refractory. Slight contamination
apparently has little effect on tile flammable characteristics of chips,
turnings, or powder produced in machining operations. However,
such contaminations should be avoided because of effects during
acid treatment, in salt baths, or exposure in nuclear reactors.
B-4.3 At temperatures considerably below its melting point,
zirconium or zirconium sponge readily combines with oxygen,
nitrogen, carbon dioxide, hydrogen, and water vapor. Surface
discoloration can indicate such contamination. Contaminated
sponge can present an increased combustion hazard.
B-5 Special Hazards.
B-5.1 A cloud of zirconium dust in air presents a serious flash fire
bazard, as well as a potential explosion hazard. Accumulations of
static dust on horizontal and vertical surfaces (beams, walls, ledges,
ductwork, etc.) present thepotential for a more serious dust
explosion since such static dust will likely be thrown into suspension
by file disturbance created by ignition of a dust cloud in the same
are~ Therefore, file importance of preventing a n d controlling any
dispersions of zirconium dust or powder warrants special emphasis.
Provision of inert atmospheres in equipment and storage containers
and die use of special cleaning e q u i p m e n t are two methods which
aid in preventing explosions. Any dust deposits produced
accidentally should be promptly cleaned up and dae affected area
washed down. All collected dust should be kept in small containers
[ 1 gal (3.8 L) maximum] under water until disposal. Needless to
say, good housekeeping and prevention of ignition sources in areas
where zirconium powder is handled are essential.
13-5.2 The burning rate of zirconium chips and turnings increases
when water or water-soluble oils are present as a surface coating.
The burning rate also increases with increasing pile depth, degree of
confinement, and increasing void space in the pile. Chips and
turnings less than 0.003 in. (0.8 ram) thick are particularly
susceptible to rapid burning. Other factors being equal, partially
wet material ignites more easily a n d burns more rapidly than dry
material.
13-5.3 Small amounts of water tend to increase the risk of explosion.
Additional beat is liberated on formation of the hydrated oxide, thus
increasing die chance of an explosion. Scrap that is fully immersed
in water will generally not overheat because the water provides a
substantial heat sink. However, with tight-packed, very finely divided
zirconium, it would seem that some risk might still be present.
B-5.4 Explosions can occur, while specimens of uranium. . alloys of 1
percent to 50 percent zirconium are immersed in nltrlC acid or while
subsequently handling die clean, dry surface after nitric acid
pickling. Formation of such explosive surface coatings can be
mitigated by providing fluoride ions in the pickling bath. Tile
fluoride should be present as 30 grams of a m m o n i u m fluoride per
liter of 50 p e r c e n t nitric acid/50 percent water solution.
B-5.5 There are incipient hazards with file collected zirconium
particulate mixed with ordinary combustibles during cleanup or
mixed with laundry. Depending on the particular problems
generated, there must be m a n a g e m e n t techniques developed to
mitigate any hazards presented to general public entities. Any and
all zirconium-bearing wastes generated should be disposed of in
accordance with all federal, state, and local regulations.
11-5.6 With certain c o m m o n metals, such as nickel and iron,
zirconium can form eutectic mixtures which exhibit melting points
much lower than the individual metals and can result in unexpected
meltdown. The condition can be exacerbated by one or more o f the
materials being in a finely divided form.
B-6 Molten Metal and Water.
B-6.1 As with any other molten metal, a violently destructive
explosion can occur if water is present in any mold, pit, or
depression into which molten zirconium is p o u r e d or spilled. The
damage might be the result of a steam explosion, an exothermic
chemical reaction, a low-order h y d r o g e n / a i r explosion, or by a
combination of these.
B-6.2 Several violent explosions occurred in titanium melting
furnaces using consumahle electrodes. The explosions occurred
when cooling water accidentally e n t e r e d tile furnace. These
explosions are of interest to zirconium production because of the
chemical and physical silrfilarity between titanium and zirconium
and the fact that the same furnaces are used for both metals. These
329
A96 ROP
accidents resulted in the formation of a committee of industry
representatives that prepared general guidelines for tile design of
titanium and zirconium melting furnaces. Their recommendations
have been published by tile Defense Metals Information Center of
Battelle Memorial Institute and have been considered in the
development of this standard.
B-7 PicMing o f Zirconium. Several mineral acids are used in the
production of zirconium sponge and mill shapes, including
hydrochloric, nitric, sulfuric, and hydrofluoric. The acids are used
to pickle the surfaces of zirconium ingots, to clean reaction vessels
a n d copper crucibles, and for pickling and cleaning mill shapes of
zirconiiain and its alloys. Careshould-be exercised-to prevent
overheating acid baths during pickling operations to prevent
explosions. Acid supplies should be stored remote from production
faalities. --
!?,-8 Tests for Zirconium.
13-8.1 Several tests will assist in the identification of zirconium and
its alloys. It is important that other metals be separated from
zirconium alloys, if tile zirconium is to be recycled.
B-8.1.1 Spark Test. Titanium, zirconium, and hafnium produce a
very brilliant spark when held against a grinding wheel. The white
lines traced by the flying sparks end with bursts that produce several
brilliant white rays or branches.
B-8.1.2 Glass Test. The softer grades of zirconium, titanium, and
hafnium can be identified by rubbing a moistened piece of tile metal
on a piece of glass. The metal will leave distinctive grey-white marks
on the glass.
11-8.1.3 Density Test. Titanium, zirconium, and hafnium can be ^
separated [/y density measurdement. Their densities are 4.54 g / c m 3,
6.50 g / c m ~, and 13.3 g / c m a, respectively.
B-8.1.4 Spectroscope. A portable metal spectroscope will better
serve the purpose for identifying and separating zirconium alloys.
B-9 Zirconium Alloys.
B-9. l The following nuclear grade zirconium alloys are available:
UNS R60001 99.5 percent Zr; 0.05 percent max. Fe
and Cr; 0.005 percent max. H2; 0.025
percent max. N2; 0.05 percent max. C;
0.02 percent max. Hf.
UNS R60802 1.2 to 1.7 percent Sn; 0.07 to 0.2
percent Fe; 0.05 to 0.15 p e r c e n t Cr; 0.03
to 0.08 percent Ni; balance Zr.
UNS R60804 1.2 to 1.7 percent Sn; 0.18 to 0.24
percent Fe; 0.07 to 0.13 percent Cr;
balance Zr.
UNS R60901 96 percent Zr; 3 percent Nb; 1 percent
Sn.
B-9.2 Non-nuclear grades of the above alloys are available,
designated as follows and having up to 4.5 percent hafnium:
Nuclear Grade Non-Nuclear Grade
R60001 701
R60802 702
R60804 704
R60901 705 (tent.)
B-10 Applications.
B-10.1 One of the largest uses of zirconium alloys is in the nuclear
field where it is used for the cladding on fuel elements of water-
cooled power reactors.
B-10.2 Zirconium alloys are used for chemical process equipment
and chemistry laboratory equipment. They are also used as filament
material for photo flashbulbs.
B-10.3 In zirconium processing and production plants, zirconium is
used for critical parts where corrosion resistance and minimal
contamination are of extreme importance. Some typical
applications include raffinate storage vessels, venturi scrubbers,
pollution control piping and ducts, fan housings and blades, heat
exchanger shells and tubes, and other equipment exposed to
chloride attack.
 NFPA 482 -- A96 ROP
B-10.4 Zirconium is a n efficient gettering a g e n t for scavenging
hydrogen, oxygen, nitrogen, a n d carbon dioxide f r o m v a c u u m
tubes. W h e n alloyed with titanium at a ratio of 66 p e r c e n t Zr to 34
percent Ti, its gettering efficiency is increased.
B-10.5 In powder form, zirconium is used as an i n g r e d i e n t in lighter
flints a n d in tile pyrotechnic c o m p o n e n t of safety flares.
B-10.6 Zirconium sheet is f o r m e d into special crucibles used for
s o d i u m peroxide fusions c o n d u c t e d in analytical chemistry
laboratories.
B-I1 Production.
B-11.1 Zircon-bearing sand is f o u n d t h r o u g h o u t the world,
including the U n i t e d States. T h e m o s t a b u n d a n t mineral containing
zirconium is zircon; second is baddeleyite (ZrO2). At present, only
zircon is u s e d for production of zirconium.
B-ll.2 Associated with zirconium in each of t h e two ores is the
e l e m e n t h a f n i u m . In zircon, it is p r e s e n t in t h e ratio of one part
h a f n i u m to 49 parts zirconium. Most of this h a f n i u m is r e m o v e d by
liquid-liquid extraction in glass c o l u m n s before the zirconium can
be u s e d for nuclear grade alloys.
B-11.3 T h e production of zirconium begins with the m a n u f a c t u r e of
zirconium tetrachloride (ZrCI4) by high t e m p e r a t u r e reaction with
chlorine (Clg) in the presence-of a r e d u c i n g agent, usually carbon.
T h e zirconiu'm tetrachloride is m a d e into zirconium s p o n g e via the
Ka-oII process.
B-11.4 In the Kroll process, zirconium tetrachloride vapor is fed to a
steel reaction c h a m b e r containing molten m a g n e s i u m . T h e
reduction is carried o u t u n d e r an inert a t m o s p h e r e of dry a r g o n or
helium at 1292°F to 1652°F (700°C to 900°C), with m a g n e s i u m
chloride f o r m e d as a by-product Any residual m a g n e s i u m chloride
or m a g n e s i u m is vacuum-distilled f r o m the reaction chamber,
leaving b e h i n d a porous form of zirconium called "sponge."
T h e reactor is cooled to 192~F (50aC) a n d the sponge treated with
,air for a short period to reduce t h e possibility of igniting the sponge.
T h e reactor is t h e n evacuated, backfilled with inert gas, a n d cooled
to 68°F (20°C). T h e s p o n g e is t h e n removed, crushed, a n d sized.
"B-11.5 Aia electrolytic process for p r o d u c i n g zirconium is currently
u n d e r d e v e l o p m e n t In this process, zirconium tetrachloride is fed
to a fused salt bath containing s o d i u m chloride a n d o t h e r materials.
T h e zirconium p r o d u c e d is a crystalline f o r m of the metal that is
t h e n c r u s h e d a n d leached.
B-11.6 Zirconium ingot is p r o d u c e d by arc-melting a c o n s u m a b l e
electrode of c o m p a c t e d sponge (or sponge a n d alloy) in a cooled
copper crucible. Tlle m o l t e n metal is protected b y v a c u u m or an
inert a t m o s p h e r e .
330
Appendix C Referenced Publications
C-I T h e following d o c u m e n t s or portions t h e r e o f are referenced
within this standard for informational purposes only a n d thus are
n o t considered part of the r e q u i r e m e n t s of this d o c u m e n t . T h e
edition indicated for each reference is t h e c u r r e n t edition as of the
date of the NFPA issuance o f this d o c u m e n t
C-I.1 NFPA Publications. National Fire Protection Association, 1
Batterymarch Park, P.O. Box 9101, Quincy, MA 02269-9101.
NFPA 17, Standard for Dry Chemical Extinguishing Systems, 1994
edition.
NFPA 51B, Standard for Fire Prevention in Use of Cutting and Welding
Processes, 1994 edition.
NFPA 68, Guidefor Venting of Deflagrations, 1994 edition.
NFPA 69, Standard on Explosion Prever~tion Syst~qns, 1992 edition.
NFPA 77, Recommended Practiceon Static Electricity, 1993 edition.
NFPA 86, Standard for Ovens and Furnaces, 1995 editi on.
NFPA 497B, Recommended Practicefor the Classification of Class H
Hazardous (Classified) Locationsfor Electrical Installations in Chemical
Process Areas, 1991 edition.
NFPA 497M, Manual for Classification of Gases, Vapors, and Dusts for
Electrical Equiprnent in Hazardous (Classified) Locations, 1991 edition.
C-1.2 O t h e r Publications.
C-1.2.1 AMCA Publication. Air M o v e m e n t a n d Control Association,
30 West University Drive, Arlington Heights, IL 60004.
AMCA Standards H a n d b o o k 99-0410-86, Classificationfor Spark-
Resistant Construction.
C-1.2.2 Chlorine Institute Publication. T h e Chlorine Institute, Inc.,
2001 L Street NW, Washington, DC 20036.
The ChlorineManua~ 5th edition, 1986.
C-1.2.3 U.S. Bureau of Mines Publications. U.S. Bureau of Mines,
Cochrans Mill Road, Pittsburgh, PA 15236-0070.
RI 3722, Inflammability and Explosibility of Metal Powders, I. Hartman,
J. Nogy, a n d H.P~ Brown, 1943.
RI 4835, Explosive Characteristics of Titanium, Zirconium, Thorium,
Uranium, and Their Hydrides, 1951.
RI 4879, Recent Practice at the Bureau of Mines, Boulder City, NY
Plant, 1951.
RI 6516, Explosibility of Metal Powders; M. Jacobsen, A.R. Cooper, a n d
J. Nagy, 1964.
C-1.2.4 U.S. Government Publication. U.S. G o v e r n m e n t Printing
Office, S u p e r i n t e n d e n t of Documents, Washington, DC 20402.
Tiff e 29, Code of Federal Regulations, Part 1910.146.